Battery separators with improved conductance, improved batteries, systems, and related methods

ABSTRACT

In accordance with at least selected embodiments, the present disclosure or invention is directed to improved battery separators, high conductance separators, improved lead-acid batteries, such as flooded lead-acid batteries, high conductance batteries, improved systems, and/or, improved vehicles including such batteries, and/or methods of manufacture or use of such separators or batteries, and/or combinations thereof. In accordance with at least certain embodiments, the present disclosure or invention is directed to improved lead acid batteries incorporating the improved separators and which exhibit increased conductance. Particular, non-limiting examples may include lead acid battery separators having structure or features designed to improve conductance, lower ER, lower water loss, and the like.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application claiming priority to U.S.application Ser. No. 17/697,987, filed Mar. 18, 2022, which claimspriority to U.S. application Ser. No. 16/328,043, filed on Feb. 25,2019; and issued as U.S. Pat. No. 11,316,231 on Apr. 26, 2022, whichclaims priority to PCT Application No. PCTUS2017049820, filed on Sep. 1,2017, which claims the benefit of U.S. Provisional Patent App. Nos.62383076 filed on Sep. 2, 2016, and 62/385,576 filed Sep. 9, 2016.

FIELD

In accordance with at least selected embodiments, the present disclosureor invention is directed to improved battery separators, highconductance separators, separators with improved conductance, improvedlead-acid batteries, such as flooded lead-acid batteries, highconductance batteries, improved systems, and/or improved vehiclesincluding such batteries, and/or methods of manufacture or use of suchseparators, systems, or batteries, and/or combinations thereof. Inaccordance with at least certain embodiments, the present disclosure orinvention is directed to improved lead acid batteries incorporating theimproved separators and which exhibit increased or acceptableconductance especially when subjected to modern battery performance orbattery health testing, and preferably even after a certain period ofbattery storage or usage (such as cycles, months or years).

In accordance with at least selected embodiments, the present disclosureor invention is directed to novel or improved separators, batteryseparators, enhanced flooded battery separators, batteries, cells,and/or methods of manufacture and/or use of such separators, batteryseparators, enhanced flooded battery separators, cells, batteries,systems, methods, and/or vehicles using the same. In accordance with atleast certain embodiments, the present disclosure or invention isdirected to novel or improved battery separators, flooded lead acidbattery separators, or enhanced flooded lead acid battery separators forstarting lighting ignition (“SLI”) batteries, flooded batteries for deepcycle applications, and enhanced flooded batteries (“EFB”) and/orimproved methods of making and/or using such improved separators, cells,batteries, systems, vehicles, or any combination thereof. In accordancewith at least certain embodiments, the present disclosure or inventionis directed to an improved separator for enhanced flooded batteriesand/or improved methods of making and/or using such batteries havingsuch improved separators. In accordance with at least selectedembodiments, the present disclosure or invention is directed toseparators, particularly separators for enhanced flooded batterieshaving reduced electrical resistance and/or increased cold crankingamps. In addition, disclosed herein are methods, systems, and batteryseparators for enhancing battery life, reducing water loss, reducinginternal resistance, increasing wettability, reducing acidstratification, improving acid diffusion, improving cold cranking amps,improving uniformity, or any combination thereof in at least enhancedflooded batteries. In accordance with at least particular embodiments,the present disclosure or invention is directed to an improved separatorfor enhanced flooded batteries wherein the separator includesperformance enhancing additives or coatings, increased porosity,increased void volume, amorphous silica, higher oil absorption silica,higher silanol group silica, silica with an OH to Si ratio of 21:100 to35:100, reduced electrical resistance, a shish-kebab structure ormorphology, a polyolefin microporous membrane containing particle-likefiller in an amount of 40% or more by weight of the membrane andpolymer, such as ultrahigh molecular weight polyethylene, havingshish-kebab formations with extended chain crystal (shish formation) andfolded chain crystal (kebab formation) and the average repetitionperiodicity of the kebab formation from 1 nm to 150 nm, decreased sheetthickness, decreased tortuosity, and/or the like.

BACKGROUND

A lead acid battery separator is used to separate the battery's positiveand negative electrodes or plates in order to prevent an electricalshort. Such a battery separator is typically a microporous insulatorfilled with liquid electrolyte so that acid and ions may pass throughthe pores thereof. Separators can be fashioned from polyolefins such aspolyethylene and polypropylene, wood, paper, rubber, PVC, andfiberglass. In lead/acid storage batteries, such as automotive,industrial and/or deep cycle batteries, the battery separator istypically a microporous polyethylene separator having a backweb and aplurality of ribs standing on one or both sides of the backweb. See:Besenhard, J. O., Editor, Handbook of Battery Materials, Wiley-VCHVerlag GmbH, Weinheim, Germany (1999), Chapter 9, pp. 245-292. Theseparators for automotive batteries are typically made in continuouslengths and rolled, subsequently folded, and sealed along the edges toform pouches or envelopes that receive the electrodes for the batteries.The separators for industrial (or traction or deep cycle storage)batteries are typically cut to a size about the same as an electrodeplate (pieces or leaves).

Separators made from polyolefins like polyethylene typically containsilica filler to facilitate separator wetting with the hydrophilicelectrolyte. In some instances, a hydrophilic material, such as a glassmat, is attached to the separator to assist with wetting and to retainactive material coated on the positive electrode. However, contactbetween the membrane and electrode can lead to increased resistance overtime.

There remains a need for lead acid batteries that do not suffersubstantial conductivity loss over time. There also remains a need forimproved battery components, including separators that provide lead-acidbatteries that do not exhibit conductivity loss or exhibit a reducedconductivity loss over time.

SUMMARY

In accordance with at least selected embodiments, the present disclosureor invention may address the above issues or needs. In accordance withat least certain objects, the present disclosure or invention mayprovide an improved separator and/or battery which overcomes theaforementioned problems, for instance by providing enhanced floodedbatteries having reduced internal electrical resistance and increasedcold cranking amps.

In accordance with at least selected embodiments, the present disclosureor invention may address the above issues or needs and/or may providenovel or improved separators and/or enhanced flooded batteries. Inaccordance with at least selected embodiments, the present disclosure orinvention is directed to improved battery separators, high conductanceseparators, separators with improved conductance, improved lead-acidbatteries, such as flooded lead-acid batteries, high conductancebatteries, improved systems, and/or improved vehicles including suchbatteries, and/or methods of manufacture or use of such separators,systems, or batteries, and/or combinations thereof. In accordance withat least certain embodiments, the present disclosure or invention isdirected to improved lead acid batteries incorporating the improvedseparators and which exhibit increased or acceptable conductanceespecially when subjected to modern battery performance or batteryhealth testing, and preferably even after a certain period of batterystorage or usage (such as cycles, months or years).

In accordance with at least selected embodiments, the present disclosureor invention is directed to novel or improved separators, batteryseparators, enhanced flooded battery separators, batteries, cells,and/or methods of manufacture and/or use of such separators, batteryseparators, enhanced flooded battery separators, cells, and/orbatteries. In accordance with at least certain embodiments, the presentdisclosure or invention is directed to novel or improved batteryseparators, flooded lead acid battery separators, or enhanced floodedbattery separators for automobile applications, for idle start stop(“ISS”) batteries, for batteries with high power requirements, such asuninterrupted power supply (“UPS”) or valve regulated lead acid(“VRLA”), and/or for batteries with high CCA requirements, and/orimproved methods of making and/or using such improved separators, cells,batteries, systems, and/or the like. In accordance with at least certainembodiments, the present disclosure or invention is directed to animproved separator for enhanced flooded batteries and/or improvedmethods of using such batteries having such improved separators. Inaddition, disclosed herein are methods, systems and battery separatorsfor enhancing battery performance and life, reducing acidstratification, reducing internal electrical resistance, increasing coldcranking amps, and/or improving uniformity in at least enhanced floodedbatteries. In accordance with at least particular embodiments, thepresent disclosure or invention is directed to an improved separator forenhanced flooded batteries wherein the separator includes decreasedelectrical resistance, performance enhancing additives or coatings,improved fillers, increased porosity, decreased tortuosity, reducedthickness, reduced oil content, increased wettability, increased aciddiffusion, and/or the like.

In accordance with at least one embodiment, a microporous separator withdecreased tortuosity is provided. Tortuosity refers to the degree ofcurvature/turns that a pore takes over its length. Thus, a microporousseparator with decreased tortuosity will present a shorter path for ionsto travel through the separator, thereby decreasing electricalresistance. Microporous separators in accordance with such embodimentscan have decreased thickness, increased pore size, more interconnectedpores, and/or more open pores.

In accordance with at least certain selected embodiments, a microporousseparator with increased porosity, or a separator with a different porestructure whose porosity is not significantly different from a knownseparator, and/or decreased thickness is provided. An ion will travelmore rapidly though a microporous separator with increased porosity,increased void volume, reduced tortuosity, and/or decreased thickness,thereby decreasing electrical resistance. Such decreased thickness mayresult in decreased overall weight of the battery separator, which inturn decreases the weight of the enhanced flooded battery in which theseparator is used, which in turn decreases the weight of the overallvehicle in which the enhanced flooded battery is used. Such decreasedthickness may alternatively result in increased space for the positiveactive material (“PAM”) or the negative active material (“NAM”) in theenhanced flooded battery in which the separator is used.

In accordance with at least certain selected embodiments, a microporousseparator with increased wettability (in water or acid) is provided. Theseparator with increased wettability will be more accessible to theelectrolyte ionic species, thus facilitating their transit across theseparator and decreasing electrical resistance.

In accordance with at least one embodiment, a microporous separator withdecreased final oil content is provided. Such a microporous separatorwill also facilitate lowered ER (electrical resistance) in an enhancedflooded battery or system.

The separator may contain improved fillers that have increasedfriability, and that may increase the porosity, pore size, internal poresurface area, wettability, and/or the surface area of the separator. Insome embodiments, the improved fillers have high structural morphologyand/or reduced particle size and/or a different amount of silanol groupsthan previously known fillers and/or are more hydroxylated thanpreviously known fillers. The improved fillers may absorb more oiland/or may permit incorporation of a greater amount of processing oilduring separator formation, without concurrent shrinkage or compressionwhen the oil is removed after extrusion. The fillers may further reducewhat is called the hydration sphere of the electrolyte ions, enhancingtheir transport across the membrane, thereby once again lowering theoverall electrical resistance or ER of the battery, such as an enhancedflooded battery or system.

The filler or fillers may contain various species (such as polarspecies, such as metals) that increase the ionic diffusion, andfacilitate the flow of electrolyte and ions across the separator. Suchalso leads to decreased overall electrical resistance as such aseparator is used in a flooded battery, such as an enhanced floodedbattery.

The microporous separator further comprises a novel and improved poremorphology and/or novel and improved fibril morphology such that theseparator contributes to significantly decreasing the electricalresistance in a flooded lead acid battery when such a separator is usedin such a flooded lead acid battery. Such improved pore morphologyand/or fibril morphology may result in a separator whose pores and/orfibrils approximate a shish-kebab (or shish kabob) type morphology.Another way to describe the novel and improved pore shape and structureis a textured fibril morphology in which silica nodes or nodes of silicaare present at the kebab-type formations on the polymer fibrils (thefibrils sometimes called shishes) within the battery separator.Additionally, in certain embodiments, the silica structure and porestructure of a separator according to the present invention may bedescribed as a skeletal structure or a vertebral structure or spinalstructure, where silica nodes on the kebabs of polymer, along thefibrils of polymer, appear like vertebrae or disks (the “kebabs”), andsometimes are oriented substantially perpendicularly to, an elongatecentral spine or fibril (extended chain polymer crystal) thatapproximates a spinal column-like shape (the “shish”).

In some instances, the improved battery comprising the improvedseparator with the improved pore morphology and/or fibril morphology mayexhibit 20% lower, in some instances, 25% lower, in some instances, 30%lower electrical resistance, and in some instances, even more than a 30%drop in electrical resistance (“ER”) (which may reduce battery internalresistance) while such a separator retains and maintains a balance ofother key, desirable mechanical properties of lead acid batteryseparators. Further, in certain embodiments, the separators describedherein have a novel and/or improved pore shape such that moreelectrolyte flows through or fills the pores and/or voids as compared toknown separators.

In addition, the present disclosure provides improved enhanced floodedlead acid batteries comprising one or more improved battery separatorsfor an enhanced flooded battery, which separator combines for thebattery the desirable features of decreased acid stratification, loweredvoltage drop (or an increase in voltage drop durability), and increasedCCA, in some instances, more than 8%, or more than 9%, or in someembodiments, more than 10%, or more than 15%, increased CCA. Such animproved separator may result in an enhanced flooded battery whoseperformance matches or even exceeds the performance of an AGM battery.Such low electrical resistance separator may also be treated so as toresult in an enhanced flooded lead acid battery having reduced waterloss.

The separator may contain one or more performance enhancing additives,such as a surfactant, along with other additives or agents, residualoil, and fillers. Such performance enhancing additives can reduceseparator oxidation and/or even further facilitate the transport of ionsacross the membrane contributing to the overall lowered electricalresistance for the enhanced flooded battery described herein.

The separator for a lead acid battery described herein may comprise apolyolefin microporous membrane, wherein the polyolefin microporousmembrane comprises: polymer, such as polyethylene, such as ultrahighmolecular weight polyethylene, particle-like filler, and processingplasticizer (optionally with one or more additional additives oragents). The polyolefin microporous membrane may comprise theparticle-like filler in an amount of 40% or more by weight of themembrane. And the ultrahigh molecular weight polyethylene may comprisepolymer in a shish-kebab formation comprising a plurality of extendedchain crystals (the shish formations) and a plurality of folded chaincrystals (the kebab formations), wherein the average repetition orperiodicity of the kebab formations is from 1 nm to 150 nm, preferably,from 10 nm to 120 nm, and more preferably, from 20 nm to 100 nm (atleast on portions of the rib side of the separator).

The average repetition or periodicity of the kebab formations iscalculated in accordance with the following definition:

-   -   The surface of the polyolefin microporous membrane is observed        using a scanning electron microscope (“SEM”) after being        subjected to metal vapor deposition, and then the image of the        surface is taken at, for example 30,000 or 50,000-fold        magnification at 1.0 kV accelerating voltage.    -   In the same visual area of the SEM image, at least three regions        where shish-kebab formations are continuously extended in the        length of at least 0.5 μm or longer are indicated. Then, the        kebab periodicity of each indicated region is calculated.    -   The kebab periodicity is specified by Fourier transform of        concentration profile (contrast profile) obtained by projecting        in the vertical direction to the shish formation of the        shish-kebab formation in each indicated region to calculate the        average of the repetition periods.    -   The images are analyzed using general analysis tools, for        example, MATLAB (R2013a).    -   Among the spectrum profiles obtained after the Fourier        transform, spectrum detected in the short wavelength region are        considered as noise. Such noise is mainly caused by deformation        of contrast profile. The contrast profiles obtained for        separators in accordance with the present invention appear to        generate square-like waves (rather than sinusoidal waves).        Further, when the contrast profile is a square-like wave, the        profile after the Fourier transform becomes a Sine function and        therefore generates plural peaks in the short wavelength region        besides the main peak indicating the true kebab periodicity.        Such peaks in the short wavelength region can be detected as        noise.

In some embodiments, the separator for a lead acid battery describedherein comprises a filler selected from the group consisting of silica,precipitated silica, fumed silica, and precipitated amorphous silica;wherein the molecular ratio of OH to Si groups within said filler,measured by ²⁹Si-NMR, is within a range of from 21:100 to 35:100, insome embodiments, 23:100 to 31:100, in some embodiments, 25:100 to29:100, and in certain preferred embodiments, 27:100 or higher.

Silanol groups change a silica structure from a crystalline structure toan amorphous structure, since the relatively stiff covalent bond networkof Si—O has partially disappeared. The amorphous-like silicas such asSi(—O—Si)₂(—OH)₂ and Si(—O—Si)₃(—OH) have plenty of distortions, whichmay function as various oil absorption points. Therefore oilabsorbability becomes high when the amount of silanol groups (Si—OH) isincreased for the silica. Additionally, the separator described hereinmay exhibit increased hydrophilicity and/or may have higher void volumeand/or may have certain aggregates surrounded by large voids when itcomprises a silica comprising a higher amount of silanol groups and/orhydroxyl groups than a silica used with a known lead acid batteryseparator.

In accordance with at least selected embodiments, aspects or objects,the present disclosure or invention may address the above needs and/ormay be directed to improving the membrane-electrode contact andcontinuity, improving the membrane-electrode interfacial resistance,improving conductivity, providing lead acid batteries that do not suffersubstantial conductivity loss over time, providing improved batterycomponents, including separators that provide lead-acid batteries thatdo not exhibit conductivity loss over time, or combinations thereof.

In accordance with at least certain embodiments, the present disclosureor invention is directed to improved battery separators, highconductance separators, improved lead-acid batteries, such as floodedlead-acid batteries, high conductance batteries, and/or, improvedvehicles including such batteries, and/or methods of manufacture or useof such separators or batteries, and/or combinations thereof. Inaccordance with at least certain selected embodiments, the presentdisclosure or invention is directed to improved lead acid batteriesincorporating the improved separators and which exhibit increasedconductance.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide improved batteryseparators, high conductance separators, improved lead-acid batteries,such as flooded lead-acid batteries, high conductance batteries, and/or,improved vehicles including such batteries, and/or methods ofmanufacture or use of such separators or batteries, and/or combinationsthereof. In accordance with at least certain selected embodiments,aspects, or objects, the present disclosure or invention may provideimproved lead acid batteries incorporating the improved separators andwhich exhibit increased conductance. Particular, non-limiting examplesmay include lead acid battery separators having topological featuresdesigned to improve conductance, low ER membranes, low water lossmembranes, and/or the like.

In an exemplary embodiment of the present invention, a separator for alead acid battery is provided with a microporous membrane having apolyolefin polymer, a particle-like filler, and a processingplasticizer; wherein the particle-like filler is present in an amount of40% or more by weight; and wherein the polyethylene comprises polymer ina shish-kebab formation having a plurality of extended chain crystals(the shish formations) and a plurality of folded chain crystals (thekebab formations) and wherein the average repetition or periodicity ofthe kebab formations is from 1 nm to 150 nm, preferably less than 120nm. Further, the separator has a shelf life estimated static conductanceloss as compared to an initial value of less than approximately 9%, lessthan approximately 8%, less than approximately 7%, less thanapproximately 6%, and less than approximately 5%. One aspect of thepresent invention provides that the shelf life estimated staticconductance is measured at greater than 30 days of resting at standardconditions.

In certain embodiments, the average repetition or periodicity of thekebab formations is defined by: taking an image of the surface of thepolyolefin microporous membrane with a SEM, indicating at least threerectangular regions where the shish-kebab formation is continuouslyextended in the length of at least 0.5 μm or longer in the same SEMimage, and specifying the repetition or periodicity by Fourier Transformof contrast profile projected in the vertical direction to the lengthdirection of the each indicated rectangular region to calculate theaverage of the repetition periods.

In select embodiments, the filler is selected from the group consistingof silica, precipitated silica, fumed silica, and precipitated amorphoussilica; and wherein the molecular ratio of OH to Si groups within thefiller, measured by ²⁹Si-NMR, is within a range of from 21:100 to35:100, preferably 27:100 or more. In certain aspects of the presentinvention, silica is present at the kebab formations of polymer.

In certain selected aspects of the present invention, the microporousmembrane may be characterized by one of the following: a) an averagepore size of no greater than 1 μm; b) an electrical resistance less than75 mΩ·cm², or less than 70 mΩ·cm², or less than 65 mΩ·cm², or less than60 mΩ·cm², or less than 55 mΩ·cm², or less than 50 mΩ·cm², or less than45 mΩ·cm², or less than 40 mΩ·cm², or less than 35 mΩ·cm², or even less;c)an electrical resistance more than 20% less than an electricalresistance of a known separator for a flooded lead acid battery; d) aporosity greater than 50%; e) a final oil content of between about10-20% by weight, in some embodiments, about 14-20% by weight; and f)ribbing, serrated ribbing, embossed ribbing, and/or negative cross ribs;and combinations thereof.

In other aspects of the present invention, the microporous membrane maybe provided with a filler having high structural morphology. The fillermay be characterized by a) an average particle size of 5 μm or less; b)a surface area of at least 100 m²/g; c) an oil absorption rate of atleast 150 ml/100 mg, or combinations thereof.

The polyolefin polymer microporous membrane may be a polyolefin,polyethylene (such as, for example, ultra-high molecular weightpolyethylene), polypropylene, rubber, polyvinyl chloride, phenolicresins, cellulosic, synthetic wood pulp, glass fibers, synthetic fibers,natural rubbers, synthetic rubbers, latex, bisphenol formaldehyde, andcombinations thereof.

The microporous membrane may be provided with a filler to polymer weightratio of 1.5:1 to 6:1. The filler may be precipitated silica.Furthermore, the particle-like silica may be friable to such a degreethat after 30 seconds of ultra-sonication, the median silica particlesize is approximately 5.2 μm or less. In addition, the particle-likefiller may be friable to such a degree that after 60 seconds ofultra-sonication, the median silica particle size is approximately 0.5μm or less.

In some exemplary embodiments, exemplary embodiments of separators ofthe present invention may have one or more of the following: a mean poresize of at least approximately 120 nm; a diffusion coefficient of atleast approximately 1.6·10-10 at −5° C., and an electrical resistance ofapproximately 40 mΩ·cm2 or lower; a diffusion coefficient of at leastapproximately 8.8·10-10 at 30° C., and an electrical resistance ofapproximately 40 mΩ·cm2 or lower.

In certain embodiments of the present invention, a separator may beprovided with one or more of the following: a polyolefin microporousmembrane, wherein the polyolefin microporous membrane comprisespolyethylene, a particle-like filler, and a processing plasticizer,wherein the particle-like filler is friable to such a degree that after30 seconds of ultra-sonication, the median silica particle size isapproximately 5.2 μm or less; a polyolefin microporous membrane, whereinthe polyolefin microporous membrane comprises polyethylene, aparticle-like filler, and a processing plasticizer, wherein theparticle-like filler is friable to such a degree that after 60 secondsof ultra-sonication, the median silica particle size is approximately0.5 μm or less; a polyolefin microporous membrane, wherein thepolyolefin microporous membrane comprises polyethylene, a particle-likefiller, and a processing plasticizer, a diffusion coefficient of atleast approximately 1.6.10⁻¹⁰ at −5° C., and an electrical resistance ofapproximately 40 mΩ·cm² or lower; a polyolefin microporous membrane,wherein the polyolefin microporous membrane comprises polyethylene, aparticle-like filler, and a processing plasticizer, a diffusioncoefficient of at least approximately 8.8·10⁻¹⁰ at 30° C., and anelectrical resistance of approximately 40 mΩ·cm² or lower; a polyolefinmicroporous membrane, wherein the polyolefin microporous membranecomprises polyethylene, a particle-like filler, and a processingplasticizer, a diffusion coefficient of at least approximately 1.6·10⁻¹⁰at −5° C., and the particle-like filler is friable to such a degree thatafter 30 seconds of ultra-sonication, the median silica particle size isapproximately 5 μm or less; a polyolefin microporous membrane, whereinthe polyolefin microporous membrane comprises polyethylene, aparticle-like filler, and a processing plasticizer, a diffusioncoefficient of at least approximately 8.8·10⁻¹⁰ at 30° C., and theparticle-like filler is friable to such a degree that after 60 secondsof ultra-sonication, the median silica particle size is approximately0.5 μm or less; a polyolefin microporous membrane, wherein thepolyolefin microporous membrane comprises polyethylene, a particle-likefiller, and a processing plasticizer, a diffusion coefficient of atleast approximately 1.6·10⁻¹⁰ at −5° C., and a mean pore size of atleast approximately 120 nm; and a comprises polyethylene, aparticle-like filler, and a processing plasticizer, a diffusioncoefficient of at least approximately 8.8·10⁻¹⁰ at 30° C., a mean poresize of at least approximately 120 nm; and combinations thereof.

The separator above wherein the separator comprises at least one of:

-   -   one or more of a surfactant, coating, wetting agent, colorant,        antistatic additive, antioxidant, agent for reducing oxidation,        and combinations thereof; and at least one surfactant, wherein        such surfactant is a non-ionic surfactant, an anionic        surfactant, or a combination thereof.

In accordance with at least certain aspects of the present invention,lead acid batteries may be provided utilizing separators as generallydescribed herein.

In particular embodiments disclosed herein, a lead acid battery may beprovided with a polyolefin microporous membrane having polyethylene,preferably, ultrahigh molecular weight polyethylene, a particle-likefiller, and a processing plasticizer; wherein the particle-like filleris present in an amount of 40% or more by weight; and wherein thepolyethylene comprises polymer in a shish-kebab formation having aplurality of extended chain crystals (the shish formations) and aplurality of folded chain crystals (the kebab formations) and whereinthe average repetition or periodicity of the kebab formations is from 1nm to 150 nm, preferably less than 120 nm. The battery may further beprovided with a shelf life estimated cold cranking amps loss as comparedto an initial value of less than approximately 9%, less thanapproximately 8%, less than approximately 7%, less than approximately6%, and less than approximately 5%. One aspect of the present inventionprovides that the shelf life estimated static cold cranking amps ismeasured at greater than approximately 30 days of resting at standardconditions.

In select embodiments of the present invention, the lead acid batterymay be any one of the following: a flat-plate battery, a flooded leadacid battery, an enhanced flooded lead acid battery, a deep-cyclebattery, an absorptive glass mat battery, a tubular battery, an inverterbattery, a vehicle battery, a SLI battery, an ISS battery, an automobilebattery, a truck battery, a motorcycle battery, an all-terrain vehiclebattery, a forklift battery, a golf cart battery, a hybrid-electricvehicle battery, an electric vehicle battery, an e-rickshaw battery, ane-trike battery, and an e-bike battery.

In accordance with at least certain aspects of the present invention,vehicles may be provided utilizing batteries and separators as generallydescribed herein.

In particular embodiments disclosed herein, a vehicle may be providedwith a lead acid battery having a polyolefin microporous membrane havingpolyethylene, preferably, ultrahigh molecular weight polyethylene, aparticle-like filler, and a processing plasticizer; wherein theparticle-like filler is present in an amount of 40% or more by weight;and wherein the polyethylene comprises polymer in a shish-kebabformation having a plurality of extended chain crystals (the shishformations) and a plurality of folded chain crystals (the kebabformations) and wherein the average repetition or periodicity of thekebab formations is from 1 nm to 150 nm, preferably less than 120 nm.The battery may further be provided with a shelf life estimated coldcranking amps loss as compared to an initial value of less thanapproximately 9%, less than approximately 8%, less than approximately7%, less than approximately 6%, and less than approximately 5%. Oneaspect of the present invention provides that the shelf life estimatedstatic cold cranking amps is measured at greater than approximately 30days of resting at standard conditions.

In select embodiments of the present invention, the vehicle may be oneof the following: an automobile, a truck, a motorcycle, an all-terrainvehicle, a forklift, a golf cart, a hybrid-electric vehicle, an electricvehicle, an e-rickshaw, an e-trike, and an e-bike.

In accordance with at least certain aspects of the present invention, asystem may be provided utilizing batteries, separators, and batteryanalyzers as generally described herein.

In particular embodiments disclosed herein, a system may be providedwith a lead acid battery having a polyolefin microporous membrane havingpolyethylene, preferably, ultrahigh molecular weight polyethylene, aparticle-like filler, and a processing plasticizer; wherein theparticle-like filler is present in an amount of 40% or more by weight;and wherein the polyethylene comprises polymer in a shish-kebabformation having a plurality of extended chain crystals (the shishformations) and a plurality of folded chain crystals (the kebabformations) and wherein the average repetition or periodicity of thekebab formations is from 1 nm to 150 nm, preferably less than 120 nm.The system may further be provided with a battery analyzer capable ofmeasuring battery conductance. The battery may further be provided witha shelf life estimated cold cranking amps loss as measured by saidbattery analyzer, and as compared to an initial value, of less thanapproximately 9%, less than approximately 8%, less than approximately7%, less than approximately 6%, and less than approximately 5%. Oneaspect of the present invention provides that the shelf life estimatedstatic cold cranking amps is measured at greater than approximately 30days of resting at standard conditions.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide improved batteryseparators, high conductance separators, improved lead-acid batteries,such as flooded lead-acid batteries, high conductance batteries, and/or,improved vehicles including such batteries, and/or methods ofmanufacture or use of such separators or batteries, and/or combinationsthereof; improved lead acid batteries incorporating the improvedseparators and which exhibit increased conductance; lead acid batteryseparators having topological features designed to improve conductance,low ER membranes, low water loss membranes, and/or the like; andcombinations thereof as shown or described herein.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide an improved conductancebattery separator comprising a microporous polymeric membrane providinghigh conductance, wherein the membrane comprises one selected from thegroup consisting of: Low ER, Low Water Loss, a profile providing limitedcontact with or obstruction of the positive plate or PAM, a profileproviding a large acid volume adjacent the positive plate or PAM, andcombinations thereof.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide an improved separator,improving the membrane-electrode contact and continuity, improving themembrane-electrode interfacial resistance, improving conductivity,providing lead acid batteries that exhibit reduced conductivity lossover time, providing improved battery components, and combinationsthereof.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide an improved highconductance battery.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide improved batteryseparators, high conductance separators, improved lead-acid batteries,such as flooded lead-acid batteries, high conductance batteries,improved vehicles including such batteries, methods of manufacture oruse of such separators or batteries, improved lead acid batteriesincorporating the improved separators and which exhibit increasedeffective static conductance, and combinations thereof as shown ordescribed herein.

The details of one or more embodiments are set forth in the descriptionsbelow. Other features, objects, and advantages will be apparent from thedescription and from the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 includes a depiction of the pore size distribution of anembodiment of the instant invention, a lower ER separator, in comparisonwith a conventional separator.

FIG. 2 includes a depiction of the oxidation stability of an embodimentof the instant invention (sometimes referred to as the “EFS” product, anEnhanced Flooded Separator™) in comparison with a conventionalseparator. In the battery overcharge test, after 1,000 hours, theseparator according to the present invention is less brittle than thecontrol separator and thus exhibits higher elongation.

FIG. 3 includes a depiction of the electrical resistance data ofseparators prepared with different silica fillers. The silica fillersdiffer in their intrinsic oil absorption. In certain embodiments of thepresent invention, the improved separator is formed using a silicahaving an intrinsic oil absorption value of about 175-350 ml/100 g, insome embodiments, 200-350 ml/100 g, in some embodiments, 250-350 ml/100gm, and in some further embodiments, 260-320 ml/100 g, though other oilabsorption values are possible as well.

FIG. 4 includes a depiction of the electrical resistance data ofseparators prepared with different process oils. The oils differ intheir aniline point.

FIG. 5 includes a depiction of acid stratification (%) versus Hgporosity (%) for separators according to the present invention.

FIG. 6 includes a depiction of ER boil versus backweb thickness.

FIG. 7 includes an SEM image of an embodiment of a separator of theinstant invention at 50,000× magnification, while FIGS. 8A and 8B areSEM images of the same separator at 10,000× magnification. In the SEM ofFIG. 7 , the shish kebab-type morphology or textured fibril-typestructure is observed, and the pore and silica structure leaves certaincavities or pores with much less polymer webbing (in some cases almostno polymer webbing) and much fewer thick fibrils or strands ofhydrophobic polymer (in some cases almost no or no thick fibrils orstrands of hydrophobic polymer). Electrolyte and/or acid, and thereforeions pass much more readily through the pore structure observed in thisseparator shown in FIGS. 7-8B. The structure of the separator providesfree space in which acid freely moves.

FIGS. 9A and 9B include depictions of the pore size distribution ofseparator embodiments. FIG. 9A is for a control separator, while FIG. 9Bis for a low ER separator with desirable mechanical properties accordingto one embodiment of the present invention. Note that FIG. 9B can alsobe seen as part of FIG. 1 .

FIG. 10 includes a comparison of various pore size measurements for aseparator according to the instant invention with a conventionalseparator. In FIG. 10 , the bubble flow rate difference is significantin that it is measuring the through-pores of the separator and measuringthe ability of such through-pores to functionally transport ions all theway through the separator. While the mean pore size and the minimum poresize are not significantly different, the maximum pore size is greaterfor the separator according to the present invention, and the bubbleflow rate is significantly higher for the separator according to thepresent invention.

FIGS. 11A and 11B show porometry data and a depiction of the flow ofliquid through a separator in accordance with an embodiment of theinvention (FIG. 11A) in comparison with flow of liquid through a controlseparator (FIG. 11B).

FIG. 12 includes two SEMs at two different magnifications of a controlseparator made by Daramic, LLC. In these SEMs, relatively thick fibrilsor strands of hydrophobic polymer are observed. FIG. 12A is taken at alower magnification as shown in the numbers at the base of the figure.FIG. 12B is taken at a higher magnification as shown in the numbers atthe base of the figure.

FIG. 13 includes two SEMs at two different magnifications of anothercontrol separator made by Daramic, LLC. In these SEMs, areas that appearto be polymer webbing can be observed. FIG. 13A is taken at a lowermagnification as shown in the numbers at the base of the figure. FIG.13B is taken at a higher magnification as shown in the numbers at thebase of the figure.

FIG. 14A includes an SEM of a separator formed according to anembodiment of the present invention, wherein the shish-kebab polymerformation(s) are observed. FIG. 14B portrays how a Fourier transformcontrast profile (spectrum at the bottom of FIG. 14B) helps determinethe repetition or periodicity of the shish-kebab formations (seeshish-kebab formation at the top of FIG. 14B) in the separator. FIG. 14Crepresents FIG. 14B in graphical manner.

FIG. 15A includes an SEM of the inventive separator of Example 1. FIGS.15B-15D include Welch Power Spectral Density Estimate graphs showingresults from the FTIR spectral tests performed on the three shish-kebabregions (Nos. 1, 2, and 3), respectively, shown and marked in FIG. 15A,wherein the x-axis of the graphs in FIGS. 15B-15D is normalizedfrequency (xπrad/sample), and wherein the y-axis of thosegraphs=power/frequency (dB/rad/sample).

FIGS. 16A-16D are similar to FIGS. 15A-15D, respectively, but arerepresentative of the inventive separator of Example 2.

FIGS. 17A-17D are similar to FIGS. 15A-15D, respectively, but arerepresentative of the inventive separator of Example 3.

FIGS. 18A-18D are similar to FIGS. 15A-15D, respectively, but arerepresentative of the inventive separator of Example 4.

FIGS. 19A-19D are similar to FIGS. 15A-15D, respectively, but arerepresentative of the inventive separator of Example 5.

FIGS. 20A-20D are similar to FIGS. 15A-15D, respectively, but arerepresentative of the separator of Comparative Example 1 (CE1).

FIGS. 21A and 21B are similar to FIGS. 15A and 15B, respectively, butare representative of the separator of Comparative Example 2.

FIG. 22 is an SEM of the separator of Comparative Example 3.

FIGS. 23A and 23B include ²⁹Si-NMR spectra for Comparative Example 4 andExample 1, respectively.

FIGS. 24A and 24B include deconvolution of the component peaks from thespectra of FIG. 23 to determine the Q₂: Q₃: Q₄ ratios for the separatorsamples of CE4 and Example 1, respectively.

FIG. 25 illustrates a tip used to puncture test separators.

FIG. 26A is a schematic rendering of an elongation test sample. FIG. 26Billustrates a sample holder for an elongation test.

FIG. 27 shows a Nuclear Magnetic Resonance (“NMR”) tube with separatorsamples submerged in D₂O.

FIG. 28 shows the diffusion coefficients at −10° C. at Δ=20 ms for asolution of H₂SO₄ only, a reference separator, an inventive embodimentseparator, and an AGM separator.

FIG. 29A illustrates a pore size distribution of an inventive embodimentseparator.

FIG. 29B illustrates a pore size distribution of a commerciallyavailable separator.

FIG. 30 depicts the pore diameter distribution of an inventiveembodiment separator.

FIG. 31 is a chart that describes the dispersion of a new silica fillerwithin an inventive embodiment separator and a standard silica within acommercially available separator.

FIG. 32A depicts the size of a standard silica used with commerciallyavailable separators. FIG. 32B depicts the size of a silica used in aninventive embodiment of the present invention.

FIG. 33 shows the size of a new silica before and after sonication.

FIG. 34A shows the silica size before and after sonication of a silicaused in a commercially available separator, and FIG. 34B shows thesilica size before and after sonification of a silica used in aninventive embodiment separator. (See lower tables for tabulated format).FIG. 34B depicts the particle size distribution of the new silica usedin inventive separator and FIG. 34A depicts the particle sizedistribution of a standard silica used in a commercially availableseparator before sonication and after 30 seconds and after 60 seconds ofsonication. (See upper figures for graphical representation.

FIG. 35 is a graph depicting the Cold Cranking Amps (CCA) of batteriesequipped with an inventive Low ER separator (an inventive Low ER LowWater Loss separator (EFS-V), and a conventional control separator(Control).

FIGS. 36A-36E are surface images of several embodiments of ribbedseparators with different rib profiles depicted. It may be preferredthat the shown ribs are positive ribs. The angled rib pattern of FIGS.36A-36C may be a possibly preferred Daramic® RipTide™ acid mixing ribprofile that can help reduce or eliminate acid stratification in certainbatteries. As further shown in FIGS. 36A-36C, the ribs may possess oneor more sets of ribs, with each set having varying angular orientationsand locations on the separator. FIG. 36D depicts a profile of alongitudinal serrated rib pattern. FIG. 36E illustrates a profile of adiagonal offset rib pattern. The negative face could have no ribs(smooth), the same ribs, smaller such ribs, mini-ribs, longitudinalmini-ribs, transverse or cross mini-ribs or negative cross ribs (NCRs),diagonal ribs, or combinations thereof.

DETAILED DESCRIPTION

Exemplary separators as disclosed herein are preferably characterized byhaving or by providing improved conductance over time. Conductance maybe determined as cold-cranking amps (“CCA”) measured by a batteryanalyzer for determining battery conductance and estimating the CCA.Such a battery analyzer may be, for instance, the MDX-600 made byMidtronics, Inc. of Willowbrook, IL, USA. For instance, a lead-acidbattery equipped with the inventive separator can exhibit a decrease ofless than 10%, less than 9%, less than 8%, less than 7%, less than 6%,less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, orless than 0.5% CCA over a period of 30 days or more at standardconditions with no load on the battery as measured by a CCA tester.

Separators as disclosed herein are characterized by improved conductanceover time. Conductance may be determined as cold-cranking amps, measuredfor instance in a CCA tester. For instance, a lead-acid battery equippedwith the inventive separator can exhibit a decrease of less than 10%,less than 9%, less than 8%, less than 7%, less than 6%, less than 5%,less than 4%, less than 3%, less than 2%, less than 1%, or less than0.5% CCA over a period of 30 days or more at standard conditions with noload on the battery as measured by a CCA tester. In contrast, the CCAdecrease observed for conventional batteries under similar conditions isoften much greater.

The separators provided herein permit the production of batteries withreduced water loss and float currents in batteries compared to batteriesmade from conventional separators. In some embodiments, water loss canbe reduced by more than 10%, 20%, 30%, 40%, 50%, 60%, 70% or 80%. Insome embodiments, float current can be reduced by more than 10%, 20%30%, 40%, 50%, 60%, 70% or 80%. Batteries prepared using the disclosedseparators exhibit reduced internal resistance increase over time, andin some cases exhibit no increased internal resistance.

In accordance with at least selected embodiments, the present disclosureor invention is directed to improved battery separators, highconductance separators, improved lead-acid batteries, such as floodedlead-acid batteries, high conductance batteries, and/or, improvedvehicles including such batteries, and/or methods of manufacture or useof such separators or batteries, and/or combinations thereof. Inaccordance with at least certain embodiments, the present disclosure orinvention is directed to improved lead acid batteries incorporating theimproved separators and which exhibit increased conductance.

In some instances, the enhanced separators used in the presentdisclosure may have optimized profiles that have a rib surface area,compared with the rib surface area of a conventional rib profile such asa solid vertical rib profile, that is 10-90% of that conventional ribsurface area, preferably 30-70% of that conventional rib surface area,and more preferably, in some instances, 40-60% of that conventional ribsurface area. All of this depends on the rib geometry, rib spacing andthe final goal of improving the acid mixing and preventing the acidstratification, all of which are optimized.

Physical Description

An exemplary separator of the present invention may be provided with aweb of a porous membrane, such as a microporous membrane having poresless than about 5 μm, preferably less than about 1 μm, a mesoporousmembrane, or a macroporous membrane having pores greater than about 1μm. The porous membrane may preferably have a pore size that issub-micron up to 100 μm, and in certain embodiments between about 0.1 μmto about 10 μm. Porosity of the separator membrane described herein maybe greater than 50% to 60% in certain embodiments. In certain selectembodiments, the porous membrane may be flat or possess ribs that extendfrom a surface thereof. The separator may be defined by a variety ofdimensions, which will be explained in detail hereinafter. For instance,exemplary dimensions may include a backweb thickness, a total thickness,a positive rib height, and a negative rib height.

An exemplary separator is provided with a web of a porous membrane. Theseparator and membrane have a machine direction (“MD”) and across-machine direction (“CMD”), a top edge and a bottom edge (bothsubstantially parallel to the CMD), and lateral side edges (bothsubstantially parallel to the MD).

The separator is provided with a positive surface, named so because itfaces a positive electrode when the separator is disposed within abattery. One or more sets of primary or positive ribs may be providedand extend from at least a portion of the positive surface of the porousmembrane. The ribs may be solid and disposed on the membranesubstantially longitudinal, which is substantially parallel to theseparator MD. The positive ribs may also extend uniformly across theentire separator width from a lateral edge to the other lateral edge,this is known as a “universal profile.” The separator has a width thatmay range from, depending upon the type of battery in which theseparator will be used, approximately 40 mm to approximately 170 mm inat least selected embodiments.

The separator is provided with a negative surface, named so because itfaces a negative electrode when the separator is disposed within abattery. One or more sets of secondary or negative ribs may be providedand extend from at least a portion of the negative surface of the porousmembrane. The ribs may be solid and disposed in an orientation that isorthogonal to the positive ribs, which substantially parallel to theseparator CMD. As such, the ribs may be said to be disposedtransversely, laterally, or be referred to as cross ribs, ornegative-cross ribs (“NCR” or “NCRs”). The negative ribs however, neednot be orthogonal to the positive ribs. They may be the same size,larger, smaller, in the same or different pattern, or combinationsthereof.

Ribs

The ribs may be a uniform set, an alternating set, or a mix orcombination of solid, discrete broken ribs, continuous, discontinuous,angled, linear, longitudinal ribs extending substantially in a MD of theseparator, lateral ribs extending substantially in a cross-machinedirection CMD of the separator, transverse ribs extending substantiallyin a CMD of the separator, cross ribs extending substantially in across-machine direction of the separator, serrations or serrated ribs,battlements or battlemented ribs, curved or sinusoidal, disposed in asolid or broken zig-zag-like fashion, grooves, channels, textured areas,embossments, dimples, porous, non-porous, mini ribs or cross-mini ribs,and/or the like, and combinations thereof. Further, the ribs may extendfrom or into the positive side, the negative side, or both sides.

Referring now to FIGS. 36A-36E, several embodiments of ribbed separatorswith different rib profiles are depicted. It may be preferred that theshown ribs are positive ribs. The angled rib pattern of FIGS. 36A-36Cmay be a possibly preferred Daramic® RipTide™ acid mixing rib profilethat can help reduce or eliminate acid stratification in certainbatteries. In some embodiments, the ribs may be discrete broken ribswith an angular orientation relative to the separator MD. The angularorientation may be an angle between greater than zero degrees (0°) andless than 180 degrees (180°) or greater than 180 degrees (180°) and lessthan 360 degrees (360°). As further shown in FIGS. 36A-36C, the ribs maypossess one or more sets of ribs, with each set having varying angularorientations and locations on the separator. The negative face couldhave no ribs (smooth), the same ribs, smaller ribs, longitudinalmini-ribs, cross mini-ribs or NCRs, diagonal ribs, or combinationsthereof.

FIG. 36D depicts a profile of a longitudinal serrated rib pattern. FIG.36E illustrates a profile of a diagonal offset rib pattern. The negativeface could have no ribs (smooth), the same ribs, smaller ribs,longitudinal mini-ribs, cross mini-ribs or NCRs, diagonal ribs, orcombinations thereof.

As discussed above, the ribs may extend uniformly across the width ofthe separator, from lateral edge to lateral edge. This is known as auniversal profile. Alternatively, the separator may have side panelsadjacent to the lateral edges with minor ribs disposed in the sidepanel. These minor ribs may be more closely spaced and smaller than theprimary ribs. For instance, the minor ribs may be 25% to 50% of theheight of the primary ribs. The side panels may alternatively be flat.The side panels may assist in sealing an edge of the separator toanother edge of the separator as done when enveloping the separator,which is discussed hereinbelow.

In select exemplary embodiments, at least a portion of the positive ribsmay preferably have a height of approximately 50 μm to approximately 2.0mm. In some exemplary embodiments, the positive rib height may beapproximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700μm, 800 μm, 900 μm, 1.0 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, or 2.0 mm.In other exemplary embodiments, the positive rib height may be nogreater than approximately 2.0 mm, 1.8 mm, 1.6 mm, 1.4 mm, 1.2 mm, 1.0mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100μm, or 50 μm.

In certain select embodiments, the positive ribs may preferably have abase width of approximately 300 μm to approximately 750 μm. In someexemplary embodiments, the positive rib base width may be approximately300 μm, 400 μm, 500 μm, 600 μm, 700 μm, or 750 μm. In some exemplaryembodiments, the positive rib base width may be no greater thanapproximately 750 μm, 700 μm, 600 μm, 500 μm, 400 μm, or 300 μm.

Should a portion of the positive ribs be substantially straight andsubstantially parallel to one another, they may possess a spacing lengthor pitch of approximately 50 μm to approximately 20 mm. In someexemplary embodiments, the positive rib pitch may be approximately 50μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900μm, 1.0 mm, 2.0 mm, 3.0 mm, 4.0 mm, or 5.0 mm, 6.0 mm, 7.0 mm, 8.0 mm,9.0 mm, or 10.0 mm, 11.0 mm, 12.0 mm, 13.0 mm, 14.0 mm, or 15.0 mm, 16.0mm, 17.0 mm, 18.0 mm, 19.0 mm, or 20.0 mm. In other exemplaryembodiments, the positive rib pitch may be no greater than approximately20.0 mm, 19.0 mm, 18.0 mm, 17.0 mm, or 16.0 mm, 15.0 mm, 14.0 mm, 13.0mm, 12.0 mm, or 11.0 mm, 10.0 mm, 9.0 mm, 8.0 mm, 7.0 mm, or 6.0 mm 5.0mm, 4.0 mm, 3.0 mm, 2.0 mm, 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm.

In select exemplary embodiments, at least a portion of the negative ribsmay preferably have a height of approximately 5% to approximately 100%of the height of the positive ribs. In some exemplary embodiments, thenegative rib height may be approximately 5%, 10%, 15%, 20%, 25%, 30%,35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 95%, or 100% comparedto the positive rib height. In other exemplary embodiments, the negativerib height may no greater than approximately 100%, 95%, 90%, 85%, 80%,75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or5% compared to the positive rib height.

In select exemplary embodiments, at least a portion of the negative ribsmay preferably have a height of approximately 5 μm to approximately 1.0mm. In certain embodiments, the negative rib height may be approximately5 μm, 10 μm, 25 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600μm, 700 μm, 800 μm, 900 μm, 1.0 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm, or2.0 mm. In other exemplary embodiments, the positive rib height may beno greater than approximately 2.0 mm, 1.8 mm, 1.6 mm, 1.4 mm, 1.2 mm,1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm,100 μm, or 50 μm, 25 μm, 10 μm, or 5 μm.

In certain exemplary embodiments, at least a portion of the negativeribs may preferably have a base width of approximately 5 μm toapproximately 1.0 mm. For instance, the negative base width may beapproximately 5 μm, 10 μm, 25 μm, 25 μm, 75 μm, 100 μm, 150 μm, 200 μm,250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm,700 μm, 750 μm, 800 μm, 850 μm, 900 μm, 950 μm, or 1.0 mm. In otherembodiments, the negative base width may be no greater thanapproximately 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm,300 μm, 200 μm, 150 μm, 100 μm, 75 μm, 50 μm, 25 μm, 10 μm, or 5 μm.

Should a portion of the negative ribs be substantially straight andsubstantially parallel to one another, they may possess a spacing lengthor pitch of approximately 50 μm to approximately 20.0 mm. In someexemplary embodiments, the negative rib pitch may be approximately 50μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900μm, 1.0 mm, 2.0 mm, 3.0 mm, 4.0 mm, or 5.0 mm, 6.0 mm, 7.0 mm, 8.0 mm,9.0 mm, or 10.0 mm, 11.0 mm, 12.0 mm, 13.0 mm, 14.0 mm, or 15.0 mm, 16.0mm, 17.0 mm, 18.0 mm, 19.0 mm, or 20.0 mm. In other embodiments, thenegative rib pitch may be no greater than approximately 20.0 mm, 19.0mm, 18.0 mm, 17.0 mm, or 16.0 mm, 15.0 mm, 14.0 mm, 13.0 mm, 12.0 mm, or11.0 mm, 10.0 mm, 9.0 mm, 8.0 mm, 7.0 mm, or 6.0 mm 5.0 mm, 4.0 mm, 3.0mm, 2.0 mm, 1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300μm, 200 μm, 100 μm, or 50 μm.

In some select embodiments, at least a portion of the porous membranemay have negative ribs that are longitudinal or transverse orcross-ribs. The negative ribs may be parallel to the top edge of theseparator, or may be disposed at an angle thereto. For instance, thenegative ribs may be oriented approximately 0°, 5°, 15°, 25°, 45°, 60°,70°, 80°, or 90° relative to the top edge. The cross-ribs may beoriented approximately 0° to approximately 30°, approximately 30° toapproximately 45°, approximately 45° to approximately 60°, approximately30° to approximately 60°, approximately 30° to approximately 90°, orapproximately 60° to approximately 90° relative to the top edge.

Certain exemplary embodiments may possess serrations or serrated ribs.If present, they may have an average tip length of from approximately 50μm to approximately 1.0 mm. For example, the average tip length may begreater than or equal to approximately 50 μm, 100 μm, 200 μm, 300 μm,400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm.Alternatively, they may be no greater than or equal to 1.0 mm, 900 μm,800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50μm.

At least a portion of the serrations or serrated ribs may have anaverage base length of from approximately 50 μm to approximately 1.0 mm.For example, the average base length may be approximately 50 μm, 100 μm,200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0mm. Alternatively, they may be no greater than or equal to approximately1.0 mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm,100 μm, or 50 μm.

At least a portion of the serrations or serrated ribs may have anaverage height of from approximately 50 μm to approximately 1.0 mm. Forexample, the average height may be approximately 50 μm, 100 μm, 200 μm,300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1.0 mm.Alternatively, they may be no greater than or equal to approximately 1.0mm, 900 μm, 800 μm, 700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100μm, or 50 μm. For embodiments in which the serration height is the sameas the rib height, the serrated ribs may also be referred to asprotrusions. Such ranges may apply to separators for industrialtraction-type start/stop batteries, where the total thickness T_(TOTAL)of the separator may typically be about 1 mm to about 4 mm, as well asautomotive start/stop batteries, where the total thickness T_(TOTAL) ofthe separator may be a little less (e.g., typically about 0.3 mm toabout 1 mm).

At least a portion of the serrations or serrated ribs may have anaverage center-to-center pitch within a column in the machine directionof from approximately 100 μm to approximately 50 mm. For example, theaverage center-to-center pitch may be greater than or equal toapproximately 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700μm, 800 μm, 900 μm, or 1.0 mm, and in similar increments up to 50 mm.Alternatively, they may be no greater than or equal to approximately 50μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900μm, or 1.0 mm, and in similar increments up to 50 mm. In addition,adjacent columns of serrations or serrated ribs may be identicallydisposed at the same position in a machine direction or offset. In anoffset configuration, adjacent serrations or serrated ribs are disposedat different positions in the machine direction.

At least a portion of the serrations or serrated ribs may have anaverage height to base width ratio of from approximately 0.1:1.0 toapproximately 500:1.0. For example, the average height to base widthratio may be approximately 0.1:1.0, 25:1.0, 50:1.0, 100:1.0, 150:1.0,200:1.0, 250:1.0, 300:1.0, 350:1, 450:1.0, or 500:1.0. Alternatively,the average height to base width ratio may be no greater than or equalto approximately 500:1.0, 450:1.0, 400:1.0, 350:1.0, 300:1.0, 250:1.0,200:1.0, 150:1.0, 100:1.0, 50:1.0, or 0.1:1.0.

At least a portion of the serrations or serrated ribs can have averagebase width to tip width ratio of from approximately 1,000:1.0 toapproximately 0.1:1.0. For example, the average base width to tip widthratio may be approximately 0.1:1.0, 1.0:1.0, 2:1.0, 3:1.0, 4:1.0, 5:1.0,6:1.0, 7:1.0, 8:1.0, 9:1.0, 10:1.0, 15:1.0, 20:1.0, 25:1.0, 50:1.0,100:1.0, 150:1.0, 200:1.0, 250:1.0, 300:1.0, 350:1.0, 450:1.0, 500:1.0,550:1.0, 600:1.0, 650:1.0, 700:1.0, 750:1.0, 800:1.0, 850:1.0, 900:1.0,950:1.0, or 1,000:1.0. Alternatively, the average base width to tipwidth ratio may be no greater than approximately 1,000:1.0, 950:1.0,900:1.0, 850:1.0, 800:1.0, 750:1.0, 700:1.0, 650:1.0, 600:1.0, 550:1.0,500:1.0, 450:1.0, 400:1.0, 350:1.0, 300:1.0, 250:1.0, 200:1.0, 150:1.0,100:1.0, 25:1.0, 20:1.0, 15:1.0, 10:1.0, 9:1.0, 8:1.0, 7:1.0, 6:1.0,5:1.0, 4:1.0, 3:1.0, 2:1.0, 1.0:1.0, or 0.1:1.0.

Backweb Thickness

In some embodiments, the porous separator membrane can have a backwebthickness T_(BACK) from approximately 50 μm to approximately 1.0 mm. forexample, the backweb thickness T_(BACK) may be may be approximately 50μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900μm, or 1.0 mm. In other exemplary embodiments, the backweb thicknessT_(BACK) may be no greater than approximately 1.0 mm, 900 μm, 800 μm,700 μm, 600 μm, 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, or 50 μm. Thoughin certain embodiments, a very thin flat backweb thickness of 50 μm orthinner is provided, for example, between approximately 10 μm toapproximately 50 μm thick.

Envelope/Form

The separator 100 may be provided as a flat sheet, a leaf or leaves, awrap, a sleeve, or as an envelope or pocket separator. An exemplaryenvelope separator may envelope a positive electrode (“positiveenveloping separator”), such that the separator has two interior sidesfacing the positive electrode and two exterior sides facing adjacentnegative electrodes. Alternatively, another exemplary envelope separatormay envelope a negative electrode (“negative enveloping separator”),such that the separator has two interior sides facing the negativeelectrode and two exterior sides facing adjacent positive electrodes. Insuch enveloped separators, the bottom edge 103 may be a folded or asealed crease edge. Further, the lateral edges 105 a, 105 b may becontinuously or intermittently sealed seam edges. The edges may bebonded or sealed by adhesive, heat, ultrasonic welding, and/or the like,or any combination thereof.

Certain exemplary separators may be processed to form hybrid envelopes.The hybrid envelope may be provided by forming one or more slits oropenings before, during or after, folding the separator sheet in halfand bonding edges of the separator sheet together so as to form anenvelope. The length of the openings may be at least 1/50th, 1/25th,1/20th, 1/15th, 1/10th, ⅛th, ⅕th, ¼th, or ⅓rd the length of the entireedge. The length of the openings may be 1/50th to ⅓rd, 1/25th to ⅓rd,1/20th to ⅓rd, 1/20th to ¼th, 1/15th to ¼th, 1/15th to ⅕th or 1/10th to⅕th the length of the entire edge. The hybrid envelope can have 1-5,1-4, 2-4, 2-3 or 2 openings, which may or may not be equally disposedalong the length of the bottom edge. It is preferred that no opening isin the corner of the envelope. The slits may be cut after the separatorhas been folded and sealed to give an envelope, or the slits may beformed prior to shaping the porous membrane into the envelope.

Some other exemplary embodiments of separator assembly configurationsinclude: the ribs 104 facing a positive electrode; the ribs 104 facing anegative electrode; a negative or positive electrode envelope; anegative or positive electrode sleeve, a negative or positive electrodehybrid envelope; both electrodes may be enveloped or sleeved, andcombinations thereof.

Composition

Exemplary embodiments of the present invention may have formulationssubstantially similar to that disclosed in U.S. patent application Ser.No. 15/482,293, filed on 7 Apr. 2017, which is incorporated herein byreference in its entirety.

The inventive separator is preferably a porous membrane made of naturalor synthetic materials, such as polyolefin, polyethylene, polypropylene,phenolic resin, PVC, rubber, synthetic wood pulp (SWP), glass fibers,synthetic fibers, cellulosic fibers, or combinations thereof, morepreferably a microporous membrane made from one or more thermoplasticpolymers. The thermoplastic polymer may, in principle, include allacid-resistant thermoplastic materials suitable for use in lead acidbatteries. The preferred thermoplastic polymers include polyvinyls andpolyolefins. The polyvinyls include, for example, polyvinyl chloride(PVC). The polyolefins include, for example, polyethylene, includingultrahigh molecular weight polyethylene (UHMWPE), and polypropylene. Onepreferred embodiment may include UHMWPE and a filler. In general, thepreferred separator may be made by mixing, in an extruder, filler,thermoplastic polymer, and processing plasticizer. The processingplasticizer may be a processing oil, such as petroleum oil,paraffin-based mineral oil, mineral oil, and any combination thereof.

The microporous separator is preferably made of a polyolefin, such aspolypropylene, ethylene-butene copolymer, and preferably polyethylene,more preferably high molecular weight polyethylene, i.e. polyethylenehaving a molecular weight of at least 600,000, even more preferablyultrahigh molecular weight polyethylene, i.e. polyethylene having amolecular weight of at least 1,000,000, in particular more than4,000,000, and most preferably 5,000,000 to 8,000,000 (measured byviscosimetry and calculated by Margolie's equation), a standard loadmelt index of substantially 0 (measured as specified in ASTM D 1238(Condition E) using a standard load of 2,160 g) and a viscosity numberof not less than 600 ml/g, preferably not less than 1,000 ml/g, morepreferably not less than 2,000 ml/g, and most preferably not less than3,000 ml/g (determined in a solution of 0.02 g of polyolefin in 100 g ofdecalin at 130° C.).

In accordance with at least one embodiment, the separator is made up ofan ultrahigh molecular weight polyethylene (UHMWPE) mixed with aprocessing oil and filler. In accordance with at least one otherembodiment, the separator is made up of an ultrahigh molecular weightpolyethylene (UHMWPE) mixed with a processing oil, additive and filler.

In certain selected embodiments, the separator can be prepared bycombining, by weight, about 5-15% polymer, in some instances, about 10%polymer, about 10-60% filler, in some instances, about 30% filler, andabout 30-80% processing oil, in some instances, about 60% processingoil. In other embodiments, the filler content is reduced, and the oilcontent is higher, for instance, greater than about 61%, 62%, 63%, 64%,65%, 66%, 67%, 68%, 69% or 70% by weight. The filler:polymer ratio (byweight) can be about (or can be between about these specific ranges)such as 2:1, 2.5:1, 3:1, 3.5:1, 4.0:1. 4.5:1, 5.0:1, 5.5:1 or 6:1. Thefiller:polymer ratio (by weight) can be from about 1.5:1 to about 6:1,in some instances, 2:1 to 6:1, from about 2:1 to 5:1, from about 2:1 to4:1, and in some instances, from about 2:1 to about 3:1.

Filler

The separator can contain a filler having a high structural morphology.Exemplary fillers can include: dry finely divided silica; precipitatedsilica; amorphous silica; highly friable silica; alumina; talc; fishmeal; fish bone meal; and the like, and any combination thereof. Incertain preferred embodiments, the filler is one or more silicas. Highstructural morphology refers to increased surface area. The filler canhave a high surface area, for instance, greater than 100 m²/g, 110 m²/g,120 m²/g, 130 m²/g, 140 m²/g, 150 m²/g, 160 m²/g, 170 m²/g, 180 m²/g,190 m²/g, 200 m²/g, 210 m²/g, 220 m²/g, 230 m²/g, 240 m²/g, or 250 m²/g.In some embodiments, the filler (e.g., silica) can have a surface areafrom 100-300 m²/g, 125-275 m²/g, 150-250 m²/g, or preferably 170-220m²/g. Surface area can be assessed using TriStar 3000™ for multipointBET nitrogen surface area. High structural morphology permits the fillerto hold more oil during the manufacturing process. For instance, afiller with high structural morphology has a high level of oilabsorption, for instance, greater than about 150 ml/100 g, 175 ml/100 g,200 ml/100 g, 225 ml/100 g, 250 ml/100 g, 275 ml/100 g, 300 ml/100 g,325 ml/100 g, or 350 ml/100 g. In some embodiments the filler (e.g.,silica)can have an oil absorption from 200-500 ml/100 g, 200-400 ml/100g, 225-375 ml/100 g, 225-350 ml/100 g, 225-325 ml/100 g, preferably250-300 ml/100 g. In some instances, a silica filler is used having anoil absorption of 266 ml/100 g. Such a silica filler has a moisturecontent of 5.1%, a BET surface area of 178 m²/g, an average particlesize of 23 μm, a sieve residue 230 mesh value of 0.1%, and a bulkdensity of 135 g/L.

Silica with relatively high levels of oil absorption and relatively highlevels of affinity for mineral oil becomes desirably dispersible in themixture of polyolefin (such as polyethylene) and mineral oil whenforming a lead acid battery separator of the type shown herein. In thepast, some separators have experienced the detriment of poordispersibility caused by silica aggregation when large amounts of silicaare used to make such separators or membranes. In at least certain ofthe inventive separators shown and described herein, the polyolefin,such as polyethylene, forms a shish-kebab structure, since there are fewsilica aggregations or agglomerates that inhibit the molecular motion ofthe polyolefin at the time of cooling the molten polyolefin. All of thiscontributes to improved ion permeability through the resulting separatormembrane, and the formation of the shish-kebab structure or morphologymeans that mechanical strength is maintained or even improved while alower overall ER separator is produced.

In some selected embodiments, the filler has an average particle size nogreater than 25 μm, in some instances, no greater than 22 μm, 20 μm, 18μm, 15 μm, or 10 μm. In some instances, the average particle size of thefiller particles (such as silica) is 15-25 μm. The particle size of thesilica filler contributes to the oil absorption of the silica and/or thesurface area of the silica filler.

In some preferred embodiments, the silica used to make the inventiveseparators has an increased amount of or number of surface silanolgroups (surface hydroxyl groups) compared with silica fillers usedpreviously to make lead acid battery separators. For example, the silicafillers that may be used with certain preferred embodiments herein maybe those silica fillers having at least 10%, at least 15%, at least 20%,at least 25%, at least 30%, or at least 35% more silanol and/or hydroxylsurface groups compared with known silica fillers used to make knownpolyolefin lead acid battery separators.

The ratio (Si—OH)/Si of silanol groups (Si—OH) to elemental silicon (Si)can be measured, for example, as follows.

-   -   1. Freeze-crush a polyolefin microporous membrane (where certain        inventive membranes contain a certain variety of oil-absorbing        silica according to the present invention), and prepare the        powder-like sample for the solid-state nuclear magnetic        resonance spectroscopy (²⁹Si—NMR).    -   2. Perform the ²⁹Si-NMR to the powder-like sample, and observe        the spectrums including the Si spectrum strength which is        directly bonding to a hydroxyl group (Spectrum: Q₂ and Q₃) and        the Si spectrum strength which is only directly bonding to an        oxygen atom (Spectrum: Q₄), wherein the molecular structure of        each NMR peak spectrum can be delineated as follows:        -   Q₂: (SiO)₂—Si*—(OH)₂: having two hydroxyl groups        -   Q₃: (SiO)₃—Si*—(OH): having one hydroxyl group        -   Q₄: (SiO)₄—Si*: All Si bondings are SiO            Where Si* is proved element by NMR observation.    -   3. The conditions for ²⁹Si-NMR used for observation are as        follows:        -   Instrument: Bruker BioSpin Avance 500        -   Resonance Frequency: 99.36 MHz        -   Sample amount: 250 mg        -   NMR Tube: 7 mφ        -   Observing Method: DD/MAS        -   Pulse Width: 45°        -   Repetition time: 100 sec        -   Scans: 800        -   Magic Angle Spinning: 5,000 Hz        -   Chemical Shift Reference: Silicone Rubber as −22.43 ppm            (External Ref)    -   4. Numerically, separate peaks of the spectrum, and calculate        the area ratio of each peak belonging to Q₂, Q₃ and Q₄. After        that, based on the ratios, calculate the molar ratio of hydroxyl        groups (—OH) bonding directly to Si. The conditions for the        numerical peak separation is conducted in the following manner:        -   Fitting region: −80 to −130 ppm        -   Initial peak top: −93 ppm for Q₂, −101 ppm for Q₃, −111 ppm            for Q₄, respectively.        -   Initial full width half maximum: 400 Hz for Q₂, 350 Hz for            Q₃, 450 Hz for Q₄, respectively.        -   Gaussian function ratio: 80% at initial and 70 to 100% while            fitting.    -   5. The peak area ratios (Total is 100) of Q₂, Q₃, and Q₄ are        calculated based on the each peak obtained by fitting. The NMR        peak area corresponded to the molecular number of each silicate        bonding structure (thus, for the Q₄ NMR peak, four Si—O—Si bonds        are present within that silicate structure; for the Q₃ NMR peak,        three Si—O—Si bonds are present within that silicate structure        while one Si—OH bond is present; and for the Q₂ NMR peak, two        Si—O—Si bonds are present within that silicate structure while        two Si—OH bonds are present). Therefore each number of the        hydroxyl group (—OH) of Q₂, Q₃, and Q₄ is multiplied by two (2)        one (1), and zero (0), respectively. These three results are        summed. The summed value displays the mole ratio of hydroxyl        groups (—OH) directly bonding to Si.

In some selected embodiments, use of the fillers described above permitsthe use of a greater proportion of processing oil during the extrusionstep. As the porous structure in the separator is formed, in part, byremoval of the oil after the extrusion, higher initial absorbed amountsof oil results in higher porosity or higher void volume. Whileprocessing oil is an integral component of the extrusion step, oil is anon-conducting component of the separator. Residual oil in the separatorprotects the separator from oxidation when in contact with the positiveelectrode. The precise amount of oil in the processing step may becontrolled in the manufacture of conventional separators. Generallyspeaking, conventional separators are manufactured using 50-70%processing oil, in some embodiments, 55-65%, in some embodiments,60-65%, and in some embodiments, about 62% by weight processing oil.Reducing oil below about 59% is known to cause burning due to increasedfriction against the extruder components. However, increasing oil muchabove the prescribed amount may cause shrinking during the drying stage,leading to dimensional instability. Although previous attempts toincrease oil content resulted in pore shrinkage or condensation duringthe oil removal, separators prepared as disclosed herein exhibitminimal, if any, shrinkage and condensation during oil removal. Thus,porosity can be increased without compromising pore size and dimensionalstability, thereby decreasing electrical resistance.

In certain selected embodiments, the use of the filler described aboveallows for a reduced final oil concentration in the finished separator.Since oil is a non-conductor, reducing oil content can increase theionic conductivity of the separator and assist in lowering the ER of theseparator. As such, separators having reduced final oil contents canhave increased efficiency. In certain selected embodiments are providedseparators having a final processing oil content (by weight) less than20%, for example, between about 14% and 20%, and in some particularembodiments, less than 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%,9%, 8%, 7%, 6%, or 5%.

Friability

In accordance with at least one embodiment, the separator is made up ofpolyethylene, such as an ultrahigh molecular weight polyethylene(“UHMWPE”), mixed with a processing oil and filler as well as anydesired additive. In accordance with at least one other embodiment, theseparator is made up of an ultrahigh molecular weight polyethylene(UHMWPE) mixed with a processing oil and talc. In accordance with atleast one other embodiment, the separator is made up of UHMWPE mixedwith a processing oil and silica, for instance, precipitated silica, forinstance, amorphous precipitated silica. The additive can then beapplied to the separator via one or more of the techniques describedabove.

Besides reducing electrical resistance and increasing cold crankingamps, preferred separators are also designed to bring other benefits.With regard to assembly, the separators are more easily passed throughprocessing equipment, and therefore more efficiently manufactured. Toprevent shorts during high speed assembly and later in life, theseparators have superior puncture strength and oxidation resistance whencompared to standard PE separators. Combined with reduced electricalresistance and increased cold cranking amps, battery manufacturers arelikely to find improved and sustained electrical performance in theirbatteries with these new separators.

In certain select embodiments, exemplary separators may utilize a silicawith a higher friability as compared to that used in commerciallyavailable separators. Silica with a high friability is believed toincrease the dispersibility of the silica within the separator, which inturn allows for more oil to penetrate the separator during formation,and, upon oil extraction, leads to a better distribution of pores withinthe separator. Lower primary silica particle size is believed to resultin greater particle aggregation, which leads to increased oilabsorption. This leads to a lower average pore size and high pore volumewith a low and narrow particle size distribution. A possibly preferredembodiment has a high silica modulus (SiO₂/Na₂O) and a greaterconcentration of sodium silicate during silica processing.

FIG. 32 depicts the size of a standard silica with that of a silica usedin an inventive embodiment of the present invention. As can be seen, thenew silica possesses a lower particle size. One way to determine thefriability of the silica is to subject the silica to an ultrasonicfrequency (over 20 kHz). FIG. 33 shows the silica size before and afterultra-sonication, and FIG. 34 depicts the particle size distribution ofthe new silica and standard silica before ultra-sonication and after 30seconds and 60 seconds of ultra-sonication.

Exemplary separators in accordance with the present disclosure also showsuperior shrinkage values in H₂SO₄. Table 1, below, shows these values.

TABLE 1 Standard Sample Average Minimum Maximum Deviation Sample #1−1.4% −2.1% −0.6% 0.3 Sample #2 −1.2% −1.6% −0.7% 0.2

In certain selected embodiments, the filler can be an alumina, talc,silica, or a combination thereof. In some embodiments, the filler can bea precipitated silica, and in some embodiments, the precipitated silicais amorphous silica. In some embodiments, it is preferred to useaggregates and/or agglomerates of silica which allow for a finedispersion of filler throughout the separator, thereby decreasingtortuosity and electrical resistance. In certain preferred embodiments,the filler (e.g., silica) is characterized by a high level offriability. Good friability enhances the dispersion of the fillerthroughout the polymer during extrusion of the microporous membrane,enhancing porosity and thus overall ionic conductivity through theseparator.

Friability may be measured as the ability, tendency or propensity of thesilica particles or material (aggregates or agglomerates) to be brokendown into smaller sized and more dispersible particles, pieces orcomponents. As shown on the left side of FIG. 34 , the NEW silica ismore friable (is broken down into smaller pieces after 30 seconds andafter 60 seconds of ultra-sonication) than the STANDARD silica. Forexample, the NEW silica had a 50% volume particle diameter of 24.90 umat 0 seconds ultra-sonication, 5.17 um at 30 seconds and 0.49 um at 60seconds. Hence, at 30 seconds ultra-sonication there was over a 50%reduction in size (diameter) and at 60 seconds there was over a 75%reduction in size (diameter) of the 50% volume silica particles. Hence,one possibly preferred definition of “high friability” may be at least a50% reduction in average size (diameter) at 30 seconds ofultra-sonication and at least a 75% reduction in average size (diameter)at 60 seconds of ultra-sonication of the silica particles (or inprocessing of the resin silica mix to form the membrane). In at leastcertain embodiments, it may be preferred to use a more friable silica,and may be even more preferred to use a silica that is friable andmulti-modal, such as bi-modal or tri-modal, in its friability. Withreference to FIG. 34 , the STANDARD silica appears single modal in itfriability or particle size distribution, while the NEW silica appearsmore friable, and bi-modal (two peaks) at 30 seconds ultra-sonicationand tri-modal (three peaks) at 60 seconds ultra-sonication. Such friableand multi-modal particle size silica or silicas may provide enhancedmembrane and separator properties.

The use of a filler having one or more of the above characteristicsenables the production of a separator having a higher final porosity.The separators disclosed herein can have a final porosity greater than60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70%. Porosity maybe measured using gas adsorption methods. Porosity can be measured byBS-TE-2060.

In some selected embodiments, the microporous separator can have agreater proportion of larger pores while maintaining the average poresize no greater than about 1 μm, 0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm,or 0.1 μm.

Additives

The separator may contain one or more performance enhancing additives,such as surfactants, wetting agents, colorants, antistatic additives,antioxidants, and/or the like, and combinations thereof. The performanceenhancing additive may preferably be a surfactant. Certain suitablesurfactants are nonionic while other suitable surfactants are anionic.The use of these certain suitable surfactants in conjunction with theinventive separators described herein can lead to even further improvedseparators that, when used in a lead acid battery, lead to reduced waterloss for that lead acid battery. Suitable surfactants includesurfactants such as salts of alkyl sulfates; alkylarylsulfonate salts;alkylphenol-alkylene oxide addition products; soaps;alkyl-naphthalene-sulfonate salts; one or more sulfo-succinates, such asan anionic sulfo-succinate; dialkyl esters of sulfo-succinate salts;quaternary amines; block copolymers of ethylene oxide and propyleneoxide; and salts of mono and dialkyl phosphate esters. The additive canbe a non-ionic surfactant such as polyol fatty acid esters,polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharidessuch as alkyl polyglycosides and blends thereof, amine ethoxylates,sorbitan fatty acid ester ethoxylates, organosilicone based surfactants,ethylene vinyl acetate terpolymers, ethoxylated alkyl aryl phosphateesters and sucrose esters of fatty acids.

The battery separators can be provided in various ways with theadditive(s), agent(s), and/or filler(s). The additive or additives canfor example be applied to the separator when it is finished (e.g., afterthe extraction of the plasticizer (e.g., processing oil)) and/or addedto the mixture used to extrude and ultimately produce the separator.According to certain preferred embodiments, the additive or a solutionof the additive is applied to the surface of the separator. This variantis suitable in particular for the application of non-thermostableadditives and additives which are soluble in the solvent used for thesubsequent extraction. Particularly suitable as solvents for theadditives according to the invention are low-molecular-weight alcohols,such as methanol and ethanol, as well as mixtures of these alcohols withwater. The application can take place on the side facing the negativeelectrode, the side facing the positive electrode or on both sides ofthe separator. Application can also take place during the extraction ofthe pore forming agent while in a solvent bath.

Certain embodiments of separators according to the present invention donot incorporate an additive such as a non-ionic surfactant or anionicsurfactant. In other embodiments, an additive (such as a non-ionicsurfactant, or an anionic surfactant) can be present at a density of atleast 0.5 g/m², 1.0 g/m², 1.5 g/m², 2.0 g/m², 2.5 g/m², 3.0 g/m², 3.5g/m², 4.0 g/m², 4.5 g/m², 5.0 g/m², 5.5 g/m², 6.0 g/m², 6.5 g/m², 7.0g/m², 7.5 g/m², 8.0 g/m², 8.5 g/m², 9.0 g/m², 9.5 g/m², or 10.0 g/m².The additive can be present on the separator at a density between 0.5-10g/m², 1.0-10.0 g/m², 1.5-10.0 g/m², 2.0-10.0 g/m², 2.5-10.0 g/m²,3.0-10.0 g/m², 3.5-10.0 g/m², 4.0-10.0 g/m², 4.5-10.0 g/m², g/m²,5.5-10.0 g/m², 6.0-10.0 g/m², 6.5-10.0 g/m², 7.0-10.0 g/m², 7.5-10.0g/m², g/m², 5.0-11.0 g/m², 5.0-12.0 g/m², or 5.0-15.0 g/m².

The application may also take place by dipping the battery separator inthe additive or a solution of the additive (solvent bath addition) andsubsequently optionally removing the solvent, e.g. by drying. In thisway the application of the additive can be combined for example with theextraction often applied during separator production. Other preferredmethods are to spray the surface with additive or roller coat or curtaincoat additives on the surface of separator.

Another preferred option is to mix the additive or additives into themixture of thermoplastic polymer and optionally fillers and other agentsor additives which is used to produce the battery separators. Theadditive-containing homogeneous mixture is then formed into a web-shapedmaterial.

In certain embodiments, exemplary separators may contain one or moreperformance enhancing additives. The performance enhancing additive maybe surfactants, wetting agents, colorants, antistatic additives,UV-protection additives, antioxidants, and/or the like, and anycombination thereof.

Certain suitable surfactants are non-ionic while other suitablesurfactants are anionic. The additive can be a single surfactant or amixture of two or more surfactants, for instance two or more anionicsurfactants, two or more non-ionic surfactants, or at least one ionicsurfactant and at least one non-ionic surfactant. Selected suitablesurfactants may have HLB values less than 6, preferably less than 3. Theuse of these certain suitable surfactants in conjunction with theinventive separators described herein can lead to even further improvedseparators that, when used in a lead acid battery, lead to reduced waterloss, reduced antimony poisoning, improved cycling, reduced floatcurrent, reduced float potential, and/or the like, or any combinationthereof for that lead acid batteries. Suitable surfactants includesurfactants such as salts of alkyl sulfates; alkylarylsulfonate salts;alkylphenol-alkylene oxide addition products; soaps;alkyl-naphthalene-sulfonate salts; one or more sulfo-succinates, such asan anionic sulfo-succinate; dialkyl esters of sulfo-succinate salts;amino compounds (primary, secondary or tertiary amines; quaternaryamines; block copolymers of ethylene oxide and propylene oxide; variouspolyethylene oxides; and salts of mono and dialkyl phosphate esters. Theadditive can include a non-ionic surfactant such as polyol fatty acidesters, polyethoxylated esters, polyethoxylated alcohols, alkylpolysaccharides such as alkyl polyglycosides and blends thereof, amineethoxylates, sorbitan fatty acid ester ethoxylates, organosilicone basedsurfactants, ethylene vinyl acetate terpolymers, ethoxylated alkyl arylphosphate esters and sucrose esters of fatty acids.

In certain embodiments described herein, a reduced amount of, or evenvery little to no anionic or non-ionic surfactant is added to theinventive separator. In such instances, the ER of the inventiveseparator may be slightly higher than an inventive separator comprisingmore of the anionic or non-ionic surfactant; however, the combination ofthe lower ER versus known separators combined with the desirable featureof lowered total organic carbons (because of the lower amount ofsurfactant) may produce a desirable inventive separator according tosuch embodiment.

In certain embodiments, the additive can be represented by a compound ofFormula (I)

R(OR¹)_(n)(COOM_(1/x) ^(x+))_(m)  (I)

in which:

-   -   R is a non-aromatic hydrocarbon radical with 10 to 4200 carbon        atoms, preferably 13 to 4200, which can be interrupted by oxygen        atoms;    -   R¹═H, —(CH₂)_(k)COOM^(x+) _(1/x) or —(CH₂)_(k)—SO₃M^(x+) _(1/x),        preferably H, where k=1 or 2;    -   M is an alkali metal or alkaline-earth metal ion, H⁺ or NH₄ ⁺,        where not all the variables M simultaneously have the meaning        H⁺;    -   n=0 or 1;    -   m=0 or an integer from 10 to 1400; and    -   x=1 or 2.

The ratio of oxygen atoms to carbon atoms in the compound according toFormula (I) being in the range from 1:1.5 to 1:30 and m and n not beingable to simultaneously be 0. However, preferably only one of thevariables n and m is different from 0.

By non-aromatic hydrocarbon radicals is meant radicals which contain noaromatic groups or which themselves represent one. The hydrocarbonradicals can be interrupted by oxygen atoms, i.e. contain one or moreether groups.

R is preferably a straight-chain or branched aliphatic hydrocarbonradical which can be interrupted by oxygen atoms. Saturated,uncross-linked hydrocarbon radicals are quite particularly preferred.

Through the use of the compounds of Formula (I) for the production ofbattery separators, they can be effectively protected against oxidativedestruction.

Battery separators are preferred which contain a compound according toFormula (I) in which:

-   -   R is a hydrocarbon radical with 10 to 180, preferably 12 to 75        and quite particularly preferably 14 to 40 carbon atoms, which        can be interrupted by 1 to preferably 1 to 20 and quite        particularly preferably 1 to 8 oxygen atoms, particularly        preferably a hydrocarbon radical of formula        R²—[(OC₂H₄)_(p)(OC₃H₆)_(q)]—, in which:        -   R² is an alkyl radical with 10 to 30 carbon atoms,            preferably 12 to 25, particularly preferably 14 to 20 carbon            atoms;        -   P is an integer from 0 to 30, preferably 0 to 10,            particularly preferably 0 to 4; and        -   q is an integer from 0 to 30, preferably 0 to 10,            particularly preferably 0 to 4;        -   compounds being particularly preferred in which the sum of p            and q is 0 to 10, in particular 0 to 4;    -   n=1; and    -   m=0.

Formula R²—[(OC₂H₄)_(p)(OC₃H₆)_(q)]— is to be understood as alsoincluding those compounds in which the sequence of the groups in squarebrackets differs from that shown. For example according to the inventioncompounds are suitable in which the radical in brackets is formed byalternating (OC₂H₄) and (OC₃H₆) groups.

Additives in which R² is a straight-chain or branched alkyl radical with10 to 20, preferably 14 to 18 carbon atoms have proved to beparticularly advantageous. OC₂H₄ preferably stands for OCH₂CH₂, OC₃H₆for OCH(CH₃)₂ and/or OCH₂CH₂CH₃.

As preferred additives there may be mentioned in particular alcohols(p=q=0; m=0) primary alcohols being particularly preferred, fattyalcohol ethoxylates (p=1 to 4, q=0), fatty alcohol propoxylates (p=0;q=1 to 4) and fatty alcohol alkoxylates (p=1 to 2; q=1 to 4) ethoxylatesof primary alcohols being preferred. The fatty alcohol alkoxylates arefor example accessible through reaction of the corresponding alcoholswith ethylene oxide or propylene oxide.

Additives of the type m=0 which are not, or only difficulty, soluble inwater and sulphuric acid have proved to be particularly advantageous.

Also preferred are additives which contain a compound according toFormula (I), in which:

-   -   R is an alkane radical with 20 to 4200, preferably 50 to 750 and        quite particularly preferably 80 to 225 carbon atoms;    -   M is an alkali metal or alkaline-earth metal ion, H⁺ or NH₄ ⁺,        in particular an alkali metal ion such as Li⁺, Na⁺ and K⁺ or H⁺,        where not all the variables M simultaneously have the meaning        H⁺;    -   n=0;    -   m is an integer from 10 to 1400; and    -   x=1 or 2.

In certain embodiments, suitable additives may include, in particular,polyacrylic acids, polymethacrylic acids and acrylic acid-methacrylicacid copolymers, whose acid groups are at least partly neutralized, suchas by preferably 40%, and particularly preferably by 80%. The percentagerefers to the number of acid groups. Quite particularly preferred arepoly(meth)acrylic acids which are present entirely in the salt form.Suitable salts include Li, Na, K, Rb, Be, Mg, Ca, Sr, Zn, and ammonium(NR₄, wherein R is either hydrogen or a carbon functional group).Poly(meth)acrylic acids may include polyacrylic acids, polymethacrylicacids, and acrylic acid-methacrylic acid copolymers. Poly(meth)acrylicacids are preferred and in particular polyacrylic acids with an averagemolar mass Mw of 1,000 to 100,000 g/mol, particularly preferably 1,000to 15,000 g/mol and quite particularly preferably 1,000 to 4,000 g/mol.The molecular weight of the poly(meth)acrylic acid polymers andcopolymers is ascertained by measuring the viscosity of a 1% aqueoussolution, neutralized with sodium hydroxide solution, of the polymer(Fikentscher's constant).

Also suitable are copolymers of (meth)acrylic acid, in particularcopolymers which, besides (meth)acrylic acid contain ethylene, maleicacid, methyl acrylate, ethyl acrylate, butyl acrylate and/or ethylhexylacrylate as comonomer. Copolymers are preferred which contain at least40% by weight and preferably at least 80% by weight (meth)acrylic acidmonomer; the percentages being based on the acid form of the monomers orpolymers.

To neutralize the polyacrylic acid polymers and copolymers, alkali metaland alkaline-earth metal hydroxides such as potassium hydroxide and inparticular sodium hydroxide are particularly suitable. In addition, acoating and/or additive to enhance the separator may include, forexample, a metal alkoxide, wherein the metal may be, by way of exampleonly (not intended to be limiting), Zn, Na, or Al, by way of exampleonly, sodium ethoxide.

In some cases, the additive can include a metal salt. Exemplary metalsalts include zinc and bismuth compounds, including mixtures thereof.Suitable counter ions include sulfate, hydroxide, phosphate,tetrafluoroborate and fluoride.

In some embodiments, the metal salt can be a sulfate salt such as ZnSO₄or Bi₂(SO₄)₃. Unless specified otherwise, the term “ZnSO₄” includes theanhydrous salt as well as hydrates/solvates thereof, such as ZnSO₄·7H₂O.

The metal salt can be present at a density of at least about 0.5 g/m²,1.0 g/m², 1.5 g/m², 2.0 g/m², 2.5 g/m², 3.0 g/m², 3.5 g/m², 4.0 g/m²,4.5 g/m², 5.0 g/m², 5.5 g/m², 6.0 g/m², 6.5 g/m², 7.0 g/m², 7.5 g/m²,8.0 g/m², 8.5 g/m², 9.0 g/m², 9.5 g/m² or 10.0 g/m². The metal salt canbe present on the separator at a density between about 0.5-10 g/m²,0.5-8.0 g/m², 0.5-7.0 g/m², 1.0-7.0 g/m², 1.0-6.0 g/m², 2.0-6.0 g/m²,2-5 g/m², 2-4.0 g/m², 2.5-4.0 g/m², or 2.5-3.5.0 g/m². In someembodiments, the metal salt is present at a density of about 3.0 g/m².

The microporous polyolefin can be provided in various ways with theadditive or additives. The additives can for example be applied to thepolyolefin when it is finished (i.e. after the extraction) or added tothe mixture used to produce the polyolefin. According to a preferredembodiment the additive or a solution of the additive is applied to thesurface of the polyolefin. This variant is suitable in particular forthe application of non-thermostable additives and additives which aresoluble in the solvent used for the subsequent extraction. Particularlysuitable as solvents for the additives according to the invention arelow-molecular-weight alcohols, such as methanol and ethanol, as well asmixtures of these alcohols with water. The application can take place onthe side facing the negative electrode, the side facing the positiveelectrode or on both sides of the separator.

In some embodiments, the microporous polyolefin porous membrane mayinclude a coating on one or both sides of such layer. Such a coating mayinclude a surfactant or other material. In some embodiments, the coatingmay include one or more materials described, for example, in U.S. PatentPublication No. 2012/0094183, which is incorporated by reference herein.Such a coating may, for example, reduce the overcharge voltage of thebattery system, thereby extending battery life with less grid corrosionand preventing dry out and/or water loss.

The application may also take place by dipping the microporous membranein the additive or a solution of the additive and subsequentlyoptionally removing the solvent, e.g. by drying. In this way theapplication of the additive can be combined for example with theextraction often applied during separator production.

Another preferred option is to mix the additive or additives into themixture of thermoplastic polymer and optionally fillers and otheradditives which is used to produce the porous membrane. Theadditive-containing homogeneous mixture is then formed into a web-shapedmaterial.

Diffusion

In certain select embodiments, exemplary separators may be defined ashaving a higher diffusion rate. The diffusion rate may be measured asthe rate at which an ion is able to pass through a separator, thusdescribing the ionic flow rate through a separator. It is believed thatthe higher the porosity of a separator, the higher the diffusioncoefficient. D₂O diffusion may be analyzed using Pulsed Field GradientSpin Echo (“PFGSE”). To determine the diffusion coefficient, separatorsamples are pre-soaked in D₂O with the oil having not been extractedfrom the separator samples. The separator samples are stacked in aNuclear Magnetic Resonance (“NMR”) tube submerged in D₂O as generallyshown in FIG. 27 . The NMR tube is placed under a vacuum to remove anyair bubbles, and the diffusion coefficient in the vertical direction(through the separator samples) is monitored.

The diffusion may be calculated using the Stejskal Equation, below:

${E\left( {\delta,g,\Delta} \right)} = {{\ln\frac{E}{E_{0}}} = {{- \gamma^{2}}g^{2}\delta^{2}{D\left( {\Delta - {\delta/3}} \right)}}}$

where,

-   -   E: NMR signal peak intensity    -   Y: magnetic spin ratio(depends upon nuclides)    -   g: magnetic field gradient    -   δ: applying time of field gradient and,

D _(e) =ε/τ×D ₀

where

-   -   D_(e): diffusion coefficient of a molecule inside the separator    -   D₀: diffusion coefficient of a molecule in solution    -   ε: porosity    -   T: index of pore tortuosity.

Table 2, below, shows various diffusion coefficient values at −10° C.and 30° C., for a control separator, an inventive embodiment, and 4commercially available separators at Δ=20 ms.

TABLE 2 Sample −10° C. 30° C. Control Separator 1.7 × 10⁻¹⁰ 9.1 × 10⁻¹⁰Inventive Embodiment 1.6 × 10⁻¹⁰ 8.8 × 10⁻¹⁰ Commercial Separator #1 1.7× 10⁻¹⁰ 9.0 × 10⁻¹⁰ Commercial Separator #2 1.8 × 10⁻¹⁰ 9.0 × 10⁻¹⁰Commercial Separator #3 2.1 × 10⁻¹⁰ 1.1 × 10⁻¹⁰ Commercial Separator #41.6 × 10⁻¹⁰ 8.6 × 10⁻¹⁰

FIG. 28 shows the diffusion coefficients at −10° C. at Δ=20 ms for asolution of H₂SO₄ only, a reference separator, an inventive embodimentseparator, and an AGM separator.

FIG. 29 illustrates a pore size distribution of an inventive embodimentcompared to the commercially available separator #1.This shows that theinventive embodiment has a mean pore size of 120 nm, while thecommercially available separator has a mean pore size of only 109 nm.

FIG. 30 depicts the pore diameter distribution of an inventiveembodiment separator. FIG. 31 illustrates a chart that describes thedispersion of a new silica filler within an inventive embodimentseparator and a standard silica within a commercially separator #1.Where the box plot represents the distribution between the 25thpercentile (Q1) and the 75th percentile (Q3). In this chart, the lowerthe values, the better the silica distribution.

Electrical Resistance

In certain selected embodiments, the disclosed separators exhibitdecreased electrical resistance, for instance, an electrical resistanceno greater than about 200 mΩ·cm², 180 mΩ·cm², 160 mΩ·cm², 140 mΩ·cm²,120 mΩ·cm², 100 mΩ·cm², 80 mΩ·cm², 60 mΩ·cm², 50 mΩ·cm², 40 mΩ·cm², 30mΩ·cm², or 20 mΩ·cm². In various embodiments, the separators describedherein exhibit about a 20% or more reduction in ER compared with a knownseparator of the same thickness. For example, a known separator may havean ER value of 60 mΩ·cm²; thus, a separator according to the presentinvention at the same thickness would have an ER value of less thanabout 48 mΩ·cm².

To test a sample separator for ER testing evaluation in accordance withthe present invention, it must first be prepared. To do so, a sampleseparator is preferably submerged in a bath of demineralized water, thewater is then brought to a boil and the separator is then removed after10 minutes in the boiling demineralized water bath. After removal,excess water is shaken off the separator and then placed in a bath ofsulfuric acid having a specific gravity of 1.280 at 27° C.±1° C. Theseparator is soaked in the sulfuric acid bath for 20 minutes. Theseparator is then ready to be tested for electrical resistance.

Puncture Resistance

In certain selected embodiments, exemplary separators may becharacterized with an increased puncture resistance. For instance apuncture resistance of approximately 9 N or higher, 9.5 N or higher, 10N or higher, 10.5 N or higher, 11 N or higher, 11.5 N or higher 12 N orhigher, 12.5 N or higher, 13 N or higher, 13.5 N or higher, 14 N orhigher, 14.5 N or higher, 15 N or higher, 15.5 N or higher, 16 N orhigher, 16.5 N or higher, 17 N or higher, 17.5 N or higher, 18 N orhigher, 18.5 N or higher, 19 N or higher, 19.5 N or higher, or 20 N orhigher. In certain embodiments, exemplary separators may be preferablydefined with a puncture resistance of approximately 9 N-20 N or higher,or more preferably approximately 12 N-20 N or higher.

The puncture resistance may be measured as the force required topuncture the porous membrane utilizing the tip 100 as generally depictedin FIG. 25 . The puncture base in which the porous membrane is supportedwhile the tip 100 punctures the membrane may generally be described as abase having a 6.5 mm diameter straight hole with a 10 mm depth. Thetravel limit of the tip may be approximately 4 mm-8 mm below thepuncture base surface. The puncture tip 100 is linearly moved into themembrane at a rate of approximately 5 mm/s.

EXAMPLES

The following examples further illustrate at least selected separatorembodiments of the instant invention.

In certain embodiments, the following precipitated silicas can beemployed to obtain separators according to the invention:

Median particle size 20.48 μm, mean particle size, 24.87 μm (as measuredusing Coulter LS230)

Silica samples shown below in Table 3 having the followingcharacteristics were employed in the preparation of separators:

TABLE 3 Oil Absorption Surface Area Tap Density ml/100 g m²/g g/l SilicaA 225 180 170 Silica B 275 180 140

Polyethylene separators made using the above silica had the followingproperties shown below in Tables 4 and 5:

TABLE 4 Product Properties Unit Separator 1 Separator 2 Backwebthickness mm 0.250 0.250 Silica type Silica A Silica B Si/PE ratio 2.6:12.6:1 Starting oil content % 64.0 67.0 Final oil content % 15.5 16.5Basis weight g/m² 161 157 Puncture resistance N 14.1 13.1 Porosity %61.5 65.1 Wettability Sec 49 29 ER 10 min boil mΩ · cm² 49 40 ER 20 minsoak mΩ · cm² 65 50 Elongation - MD % 23 25 Elongation - CMD % 430 484Perox 20 hrs % 388 350 Perox 40 hrs % 333 283 Acid shrinkage % −0.9 −0.8Hg-Pore Size μm 0.099 0.126

TABLE 5 Separator 3 (Corresponds to Product Example 3 in Properties UnitTable 9 Below) Separator 4 Separator 5 Separator 6 Profile Ribbed PE,Ribbed PE, Ribbed PE, Ribbed PE, greater than 12 greater than 12 fewerthan 12 fewer than 12 major ribs, lower major ribs, lower major ribs,higher major ribs, higher rib height rib height rib height rib heightBackweb μm 250 250 250 250 thickness Silica type B A B A Si/PE ratio2.6:1 2.6:1 2.6:1 2.6:1 Starting oil % 67 64 67 64 content Final oil %16.0 16.3 15.0 16.7 content Coating NI (non-ionic) None NI (non-ionic)None Surfactant Surfactant Porosity % 63.8 61.7 64.4 60.6 Electrical mΩ· cm² 42 50 45 62 Resistance 20 minute mΩ · cm² 43 55 46 65 soak ERWettability sec 6 39 10 73 Puncture N 12.9 14.7 12.2 13.9 ResistanceElongation - % 528 419 587 383 CMD Acid % −0.7 −0.8 −0.3 −0.1 Shrinkage

Additionally, in further embodiments, the following silica fillers,described below in Table 6, were employed in the separators described inTable 7, below:

TABLE 6 Silica C Silica D Silica E Silica F Oil Absorption ml/100 g 245215 270 210 Surface Area m²/g 180 130 195 180 Bulk Density g/l 100 125No data No data

TABLE 7 Sepa- Sepa- Sepa- Sepa- rator rator rator rator 7 8 9 10 BackwebThickness mm 0.200 0.206 0.200 0.201 Silica Type C D E F Si/PE ratio2.6:1 2.6:1 2.6:1 2.6:1 Starting oil content % 68.0 65.1 67.0 65.2 BasisWeight g/m² 109.6 122.4 122.0 125.3 Final oil content % 15.1 16.4 15.814.9 Porosity % 65.9 63.6 65.7 63.4 ER 10′ Boil mΩ · cm² 36 46 33 48Wettability sec 2 2 4 3 Elongation - CMD % 275 329 294 311 PunctureResistance N 12.4 13.0 10.8 13.9

Further Examples

In the following set of examples, inventive enhanced flooded separatorswere made according to various embodiments of the present invention andtested compared with a control separator. The results are shown justbelow in Table 8.

TABLE 8 Example A Example B Enhanced Enhanced Flooded Control FloodedSPEC Property Separator A Separator A Separator B (BS-DA-961-4) ProfileRibbed PE, Ribbed PE, Ribbed PE, — fewer than 12 fewer than 12 greaterthan 12 major ribs major ribs major ribs, lower rib height Backwebthickness (mm) 0.256 0.257 0.253  0.250 ± 0.040 Puncture resistance (N)12.5 12.2 — Min. 10.0 Total oil content (%) 15.3 16.1 14.9 17.0 ± 3.0Backweb oil content (%) 14.4 14.4 — Min. 8.0 CMD elongation (%)  530(100%)  482 (100%) — Min. 150 Elongation after Perox 379 (72%) 355 (74%)— Min. 100 20 h (%) Elongation after Perox 165 (31%) — — — 40 h (%) ER10′ boil (mΩ · cm²) 71 86 65 Max. 140 Wettability (sec) 45 141 39 —Porosity (%) 64.3 57.6 65.5 60.0 ± 7.5

The results above in Table 8 show that the separator of Example Aexhibited almost 20% lower ER compared with the control separator A.Similarly, the separator of Example B exhibited more than 20% lower ERcompared with the control separator A. These desirable lower ER resultsoccurred despite the fact that the porosity percentages for theinventive separators A and B were within the tolerances (60%+/−7.5%) forthe porosity of such a separator. Thus, the novel and unexpected porestructure of the separator contributed to the lowered ER combined with aporosity percentage for the separator that is in line with (not muchmore than) the porosity of a known separator.

Additional Examples

Several separators were formed according to the present invention. Thoseseparators were compared to comparative separators. SEMs of theinventive separators were taken to image the shish-kebab formations ofthe inventive separators.

Example 1

In Example 1, an enhanced flooded separator having a backweb thicknessof 250 μm was made according to the present invention using UHMWPE,silica, and oil, and the silica used was a high oil absorption silica.An SEM of the inventive, low ER separator, was taken, see FIG. 15A.

Three shish-kebab regions, numbered Nos. 1, 2 and 3 respectively, wereidentified on the SEM of FIG. 15A, the SEM of the separator ofExample 1. Then, FTIR spectra profiles were taken of each of the threeshish-kebab regions, see FIGS. 15B-15D. The FTIR spectra taken of eachof the three shish-kebab regions (Nos. 1, 2, and 3) of the SEM of FIG.15A of the separator of Example 1 revealed the following peak positioninformation and periodicity or repetition of the shish-kebab formationsor morphology, shown in Table 9, below.

TABLE 9 Shish-kebab region number No. 1 No. 2 No. 3 Peak position 0.11720.1484 0.1094 Periodicity or 0.057 (57 nm) 0.047 (47 nm) 0.085 (85 nm)repetition of the shish-kebab formation

Ultimately, an average repetition or periodicity of the shish-kebabmorphology or structure was obtained, of 63 nm.

Example 2

Further, for Example 2, an enhanced flooded separator having a backwebthickness of 200 μm was made according to the present invention, in thesame manner as Example 1 above, using UHMWPE, silica, and oil, and thesilica used was a high oil absorption silica. An SEM of the inventive,low ER separator, was taken, see FIG. 16A.

Three shish-kebab regions, numbered Nos. 1, 2 and 3 respectively, wereidentified on the SEM of FIG. 16A, the SEM of the separator of Example2. Then, FTIR spectra profiles were taken of each of the threeshish-kebab regions, see FIGS. 16B-16D. The FTIR spectra taken of eachof the three shish-kebab regions (Nos. 1, 2, and 3) of the SEM of FIG.16A of the separator of Example 2 revealed the following peak positioninformation and periodicity or repetition of the shish-kebab formationsor morphology, shown in Table 10, below.

TABLE 10 Shish-kebab region number No. 1 No. 2 No. 3 Peak position0.1172 0.1406 0.07813 Periodicity or 0.057 (57 nm) 0.047 (47 nm) 0.085(85 nm) repetition of the shish-kebab formation

Ultimately, an average repetition or periodicity of the shish-kebabmorphology or structure was obtained, of 63 nm.

Example 3

For Example 3, an enhanced flooded separator having a backweb thicknessof 250 μm was made according to the present invention, in the samemanner as Example 1 above, using UHMWPE, silica, and oil, and the silicaused was a high oil absorption silica. An SEM of the inventive, low ERseparator, was taken, see FIG. 17A.

Three shish-kebab regions, numbered Nos. 1, 2 and 3 respectively, wereidentified on the SEM of FIG. 17A, the SEM of the separator of Example3. Then, FTIR spectra profiles were taken of each of the threeshish-kebab regions, see FIGS. 17B-17D. The FTIR spectra taken of eachof the three shish-kebab regions (Nos. 1, 2, and 3) of the SEM of FIG.17A of the separator of Example 3 revealed the following peak positioninformation and periodicity or repetition of the shish-kebab formationsor morphology, shown in Table 11, below.

TABLE 11 Shish-kebab region number No. 1 No. 2 No. 3 Peak position0.0625 0.05469 0.04688 Periodicity or 0.063 (63 nm) 0.073 (73 nm) 0.085(85 nm) repetition of the shish-kebab formation

Ultimately, an average repetition or periodicity of the shish-kebabmorphology or structure was obtained, of 74 nm.

Example 4

For Example 4, an enhanced flooded separator having a backweb thicknessof 250 μm was made according to the present invention, in the samemanner as Example 1 above, using UHMWPE, silica, and oil, and the silicaused was a high oil absorption silica (a different high oil absorptionsilica from the silica used in Examples 1-3 above; each of the high oilabsorption silicas used to make the separators of Examples 1-5 rangefrom about 230 to about 280 ml/100 g). An SEM of the inventive, low ERseparator, was taken, see FIG. 18A.

Three shish-kebab regions, numbered Nos. 1, 2 and 3 respectively, wereidentified on the SEM of FIG. 18A, the SEM of the separator of Example4. Then, FTIR spectra profiles were taken of each of the threeshish-kebab regions, see FIGS. 18B-18D. The FTIR spectra taken of eachof the three shish-kebab regions (Nos. 1, 2, and 3) of the SEM of FIG.18A of the separator of Example 4 revealed the following peak positioninformation and periodicity or repetition of the shish-kebab formationsor morphology, shown in Table 12, below.

TABLE 12 Shish-kebab region number No. 1 No. 2 No. 3 Peak position0.07031 0.07031 0.07813 Periodicity or 0.056 (56 nm) 0.056 (56 nm) 0.051(51 nm) repetition of the shish-kebab formation

Ultimately, an average repetition or periodicity of the shish-kebabmorphology or structure was obtained, of 55 nm.

Example 5

For this example, Example 5, an enhanced flooded separator having abackweb thickness of 250 μm was made according to the present invention,in the same manner as Example 1 above, using UHMWPE, silica, and oil,and the silica used was a high oil absorption silica (a different highoil absorption silica from the silica used in Examples 1-3 above andfrom the silica used in Example 4 above). An SEM of the inventive, lowER separator, was taken, see FIG. 19A.

Three shish-kebab regions, numbered Nos. 1, 2 and 3 respectively, wereidentified on the SEM of FIG. 19A, the SEM of the separator of Example5. Then, FTIR spectra profiles were taken of each of the threeshish-kebab regions, see FIGS. 19B-19D. The FTIR spectra taken of eachof the three shish-kebab regions (Nos. 1, 2, and 3) of the SEM of FIG.19A of the separator of Example 5 revealed the following peak positioninformation and periodicity or repetition of the shish-kebab formationsor morphology, shown in Table 13, below.

TABLE 13 Shish-kebab region number No. 1 No. 2 No. 3 Peak position0.07031 0.0625 0.0625 Periodicity or 0.056 (56 nm) 0.063 (63 nm) 0.063(63 nm) repetition of the shish-kebab formation

Ultimately, an average repetition or periodicity of the shish-kebabmorphology or structure was obtained, of 61 nm.

Comparative Example 1

A comparative polyethylene lead acid battery separator was obtained, theseparator having a backweb thickness of 250 μm. An SEM of theComparative Example 1 separator was taken, see FIG. 20A.

Three regions, numbered Nos. 1, 2 and 3 respectively, were identified onthe SEM of FIG. 20A, the SEM of the separator of Comparative Example 1.Then, FTIR spectra profiles were taken of each of those three regions,see FIGS. 20B-20D. The FTIR spectra taken of each of the three numberedregions (Nos. 1, 2, and 3) of the SEM of FIG. 20A of the separator ofComparative Example 1 revealed the following peak position informationand periodicity or repetition information regarding the crystallinestructure and/or morphology of those three regions, shown in Table 14,below.

TABLE 14 Region number No. 1 No. 2 No. 3 Peak position 0.03906 0.039060.03906 Periodicity or 0.170 (170 nm) 0.170 (170 nm) 0.170 (170 nm)repetition of the crystalline structure of morphology of the region

Ultimately, an average repetition or periodicity of the crystallinestructure or morphology of the identified regions was obtained, of 170nm.

Comparative Example 2

Another comparative polyethylene lead acid battery separator wasobtained, the separator having a backweb thickness of 250 μm. An SEM ofthe Comparative Example 2 separator was taken, see FIG. 21A.

A region of the separator SEM image, numbered No. 1, was identified onthe SEM of FIG. 21A, the SEM of the separator of Comparative Example 2.Then, an FTIR spectra profile was taken of that region, see FIG. 21B.The FTIR spectrum taken of the region (No. 1) of the SEM of FIG. 21A ofthe separator of Comparative Example 2 revealed the following peakposition information and periodicity or repetition information regardingthe crystalline structure and/or morphology of that region, shown inTable 15, below.

TABLE 15 Region number No. 1 Peak position 0.03125 Periodicity or 0.212(212 nm) repetition of the crystalline structure of morphology of theregion

Thus, the repetition or periodicity of the crystalline structure ormorphology of the identified region was 212 nm.

Comparative Example 3

Yet another comparative polyethylene lead acid battery separator wasobtained, this one commercially available from Daramic, LLC. Theseparator had a backweb thickness of 250 μm. This separator was madesimilarly to the separators described in Examples 1-5 above, but thesilica used to make this separator was not one with a high oilabsorption value.

An SEM of the Comparative Example 3 separator was taken, see FIG. 22 .Observing FIG. 22 , there were no shish-kebab formations which werecontinuously extending in the length of at least 0.5 μm or longer inthis SEM image of the polyolefin microporous membrane. Therefore, noregions were marked on the SEM or further analyzed.

Table 16, below, compares the results obtained for the periodicity orrepetition of the shish-kebab regions of Examples 1-5 versus resultsobtained for Comparative Examples 1-3.

TABLE 16 Region Example Number Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 CE 1 CE 2CE 3 No. 1 57 nm 57 nm 63 nm 56 nm 56 nm 170 nm 212 nm — No. 2 47 nm 47nm 73 nm 56 nm 63 nm 170 nm — — No. 3 85 nm 85 nm 85 nm 51 nm 64 nm 170nm — — Average 63 nm 63 nm 74 nm 55 nm 61 nm 170 nm 212 nm —

For Examples 1-5, the average repetition or periodicity of theshish-kebab formations and/or crystalline structures and/or morphologieswas from 1 nm to 150 nm, preferably from 10 nm to 120 nm, and even morepreferably from 20 nm to 100 nm. That type of structure was not observedfor the separators of Comparative Examples 1-3.

Additional properties and features of the separators of Examples 1-2 and4-5 are shown below in Table 17 (whereas Table 3 above includesproperties of the separator of Example 3).

TABLE 17 Product Properties Unit Example 1 Example 2 Example 4 Example 5Profile Ribbed PE, Ribbed PE, Ribbed PE, Ribbed PE, greater than 12greater than 12 fewer than 12 fewer than 12 major ribs, lower majorribs, lower major ribs major ribs rib height rib height Backweb μm 250200 250 250 thickness Final oil content % 17.1 14.3 17.0 11.3 Porosity %62.5 65.8 58.7 65.2 Electrical mΩ · cm² 53 38 52 45 Resistance 20 minutesoak mΩ · cm² 57 36 — — ER Puncture N 13.6 12.7 11.6 12.0 ResistanceWettability seconds 25 8 6 6 Elongation - % 587 470 713 616 CMD AcidShrinkage % −1.4 −1.5 −0.1 −0.4

Solid State NMR Examples

For two separator samples, the ratio (Si—OH)/Si of silanol groups(Si—OH) to elemental silicon (Si) was measured using the ²⁹Sisolid-state NMR technique described in great detail above. A sample ofthe separator of Example 1 was prepared for this NMR testing as well asa sample of a comparative separator, Comparative Example 4, which was acommercially available polyethylene separator from Daramic, LLC, havinga 250 μm backweb thickness, made with the same type of polyethylenepolymer and silica as the separator described above as ComparativeExample 3.

A ²⁹Si-NMR spectrum of each sample was obtained, and these spectra areincluded as FIG. 23 . The Q₂ signal was observed at ca. −93 ppm, whilethe Q₃ signal was observed at ca. −103 ppm, and the Q₄ signal wasobserved at ca. −111 ppm. Each component peak was deconvoluted as shownin FIG. 24 , and the Q₂:Q₃:Q₄ molecular ratios were calculated usingthat information from FIG. 24 , with results shown below in Table 18:

TABLE 18 Observed ²⁹Si-NMR Signal Area Ratio Molecular Ratio Q₁ Q₂ Q₃ Q₄OH Si OH/Si CE4 0 2 16 82 20 100 0.20 Example 1 0 5 17 78 27 100 0.27Number of 3 2 1 0 OH Bonding

In the results shown above, the OH/Si ratio of the separator of Example1 is 35% higher than the OH/Si ratio for the separator of ComparativeExample 4, meaning that the additional hydroxyl and/or silanol groupspresent for the silica for the inventive separator may contribute to theimproved features of the inventive separator such as its desirable porestructure and/or morphology and its low ER.

In accordance with at least selected embodiments, the separator mayinclude or exhibit performance enhancing additives or coatings,increased porosity, increased void volume, amorphous silica, higher oilabsorption silica, fillers or silica with increased friability,increased ionic diffusion, higher silanol group silica, silica with anOH to Si ratio of 21:100 to 35:100, reduced electrical resistance, ashish-kebab structure or morphology, a polyolefin microporous membranecontaining particle-like filler in an amount of 40% or more by weight ofthe membrane and ultrahigh molecular weight polyethylene havingshish-kebab formations with extended chain crystal (shish formation) andfolded chain crystal (kebab formation) and the average repetitionperiodicity of the kebab formation from 1 nm to 150 nm, decreased sheetthickness, decreased tortuosity, and/or the like, or any combinationthereof. Such inventive separators may be especially well suited forenhanced flooded batteries (EFB) built for higher performance andreliability than conventional flooded batteries, that support at leastcertain start-stop functionality, with enhanced starting power, thatmeet the ever-increasing electrical demands of many vehicles, thatprovide a longer lifespan of recovering from deep discharges, that powerelectrical loads during engine-off periods and that support a highnumber of starts per trip, with superior cycling capability, chargeacceptance and/or the ability to operate at a low state of charge and/ora partial state of charge, with tight packed components, with batteryvibration resistance, with reliable starting performance, excellentcycling ability, improved cycling of batteries operating in a low stateand/or partial state of charge, and/or longer life than traditionallead-acid batteries, and/or the like.

Example 6

An additional example, with results shown below in Tables 19 and 20,depicts expanded battery testing data. Batteries were manufactured thenthe estimated CCA was measured. The “new” samples were batteriesutilizing a separator having a serrated positive rib profile with aformulation as substantially described herein. The “control” batteriesutilized a standard commercially available separator having solidpositive ribs. These results proved out surprisingly unexpected findingsregarding the improvement in battery performance for start/stop enhancedflooded lead-acid batteries using enhanced separators according to thepresent disclosure. Significantly and surprisingly, the results in thetable below showed improvements even when the batteries had not beenplaced into significant motion in a vehicle but rather had just been ingeneral motion while moving from place to place within a plant fortesting. Thus, combined with the motion from a vehicle and/or the energyfrom various start/stop events, the battery performance results mayimprove even more significantly. As shown in Table 19, the new sampleshad a higher discharge performance with improved quality, and improvedestimated CCA with the standard deviation.

TABLE 19 Estimated Estimated Sample CCA Voltage Sample CCA Voltage New-1930 12.98 Control-1 874 12.86 New-2 935 12.98 Control-2 902 12.86 New-3910 12.96 Control-3 884 12.86 New-4 925 12.96 Control-4 890 12.89 New-5913 12.98 Control-5 894 12.87 New-6 931 12.98 Control-6 883 12.88 New-7930 12.98 Control-7 895 12.86 New-8 933 12.98 Control-8 897 12.86 New-9934 12.98 Control-9 886 12.89 New-10 927 12.95 Control-10 928 12.89Average 927 12.97 Average 893 12.87 Std deviation 8.64 0.01 Stddeviation 14.63 0.01

Table 20, below, shows the improvement of the new samples as compared tothe control samples, with respect to the above data in Table 19.

TABLE 20 Estimated CCA Voltage New to Control Avg. 33.5 0.101Improvement New to Control 3.60% 0.80% Avg. % Improvement Std deviation−5.99 0 improvement

Example 7

Batteries were tested by measuring an estimated CCA while they sat atstandard conditions for over 30 days. Batteries using a control batteryutilizing a typical commercially available battery separator, a firstsample battery utilizing a first sample separator of the presentinvention (“sample 1”), and a second sample battery utilizing a secondsample separator of the present invention (“sample 2”). Sample 1utilized a separator as generally described herein. Sample 2 utilized aseparator as generally described herein with a wetting agent.

The batteries' estimated CCA were measured at various intervals over a34 day period of sitting at standard conditions without being charged ordischarged. Table 21 shows the estimated CCA of the Control Batteriesover a 34 day period. Table 22 shows the estimated CCA of the Sample 1Batteries over a 34 day period. Table 23 shows the estimated CCA of theSample 2 Batteries over a 34 day period. The average % loss for alltables was measured by comparing the current CCA as compared to thatmeasured on Day 2. Day 1 measurements were not available as thebatteries were in transit from the manufacturer.

TABLE 21 Day: 2 3 6 7 8 9 10 20 34 Control # 1 1032 1013 1005 997 989985 984 964 931 Battery # 2 999 988 967 964 958 958 957 937 905 # 3 1003993 975 971 971 968 964 945 913 # 4 1016 1003 980 980 974 968 968 957925 # 5 985 972 955 956 947 946 947 923 899 # 6 999 984 965 964 963 959958 937 910 Average 1006 992 975 972 967 964 963 944 914 Confidence13.02 11.56 13.80 11.73 11.57 10.48 10.02 11.92 9.69 Avg. % Loss 1.34%3.10% 3.35% 3.84% 4.14% 4.24% 6.15% 9.13%

TABLE 22 Day: 2 3 6 7 8 9 10 20 34 Sample 1 # 1 1038 1040 1004 994 992990 993 966 958 Battery # 2 1055 1050 1021 1017 1022 1013 1012 991 977 #3 1043 1030 1003 1001 1002 994 997 976 970 # 4 1046 1030 1001 999 993995 996 971 962 # 5 1047 1031 1011 1004 1003 1001 994 964 955 # 6 10181014 992 985 986 980 975 962 948 Average 1041 1033 1005 1000 1000 996995 972 962 Confidence 10.11 9.60 7.85 8.53 10.15 8.83 9.45 8.60 8.39Avg. % Loss 0.83% 3.44% 3.95% 3.99% 4.39% 4.48% 6.68% 7.64%

TABLE 23 Day: 2 3 6 7 8 9 10 20 34 Sample 2 # 1 1036 1035 1017 1008 10041003 1004 983 975 Battery # 2 1030 1020 1005 1000 996 999 999 984 977 #3 1050 1002 1022 1021 1002 1020 1016 1002 985 # 4 1009 1031 987 984 982980 975 963 954 # 5 1043 1018 1009 1006 1006 1001 1001 982 964 # 6 10251040 1003 995 996 989 991 977 974 Average 1032 1024 1007 1002 998 999998 982 972 Confidence 11.56 11.09 9.79 10.05 6.97 10.86 11.01 10.068.72 Avg. % Loss 0.76% 2.42% 2.89% 3.34% 3.25% 3.34% 4.88% 5.88%

As shown in Table 21, the Control Batteries exhibited on average agreater than 9% loss in CCA over the span of the test. Table 22 showsthe Sample 1 Batteries exhibited on average a less than 8% loss in CCAover the span of the test. Table 23 shows the Sample 2 Batteriesexhibited on average a less than 6% loss in CCA over the span of thetest. This data is graphically represented in FIG. 35 . The loss in CCAof the batteries over time can be correlated to the static conductanceloss of the separators used therein.

The significance of this battery analyzer test is that it is not aGlobal Standard test, but that these analyzers are typically hand helddevices using an algorithm to quickly and easily calculate theperformance of the battery. As such, they are typically used in thefield, such as for example at a retail store, an oil change shop, or ata mechanic's shop, to quickly assess a battery's performance and todetermine if a battery needs to be replaced.

In a Lead Acid battery certain rib profiles (broken, discontinuous,serrated, nubs, protrusions, or combinations may limit rib contactsurface area with the Positive Active Material (PAM) on the positiveelectrode. Thereby maximizing the available acid, conductivity andoverall PAM utilization, and thereby provide an improved signal with ahigher score on a battery analyzer test and also provide an improvedsignal to a Battery Management System (“BMS”) used to monitor the Stateof Health (“SOH”) in a Micro-Hybrid Start-Stop Car or UninterruptiblePower Supply (“UPS”) Data Center back up power system. This improvementis demonstrated over time as the battery rests and can be valued in twoways:

First: This will help batteries meet or exceed the stated batteryratings in which batteries are measured on the shelf for 30 days. Pointof sale locations such as auto parts and farm supply stores, garages andbattery shops are using battery analyzers to judge good or bad lead acidbatteries (new or used). Customers and purchasing agents use batteryanalyzers to make purchasing decisions after the battery is over 30 daysold.

Second: This will help the reliability of both the UPS back up power andStart-Stop system with and improved BMS communications to the batteryallowing for improved SOH resulting in improved battery energythroughput, charge acceptance, reserve capacity providing the systemwith longer engine off periods saving CO₂ emissions, or overall moreback up power time.

CONCLUSION

In accordance with at least selected embodiments, aspects or objects,the present disclosure or invention is directed to improved batteryseparators, high conductance separators, separators with improvedconductance, improved lead-acid batteries, such as flooded lead-acidbatteries, high conductance batteries, improved systems, and/or improvedvehicles including such batteries, and/or methods of manufacture or useof such separators, systems, or batteries, and/or combinations thereof.In accordance with at least certain embodiments, the present disclosureor invention is directed to improved lead acid batteries incorporatingthe improved separators and which exhibit increased or acceptableconductance especially when subjected to modern battery performance orbattery health testing, and preferably even after a certain period ofbattery storage or usage (such as cycles, months or years).

In accordance with at least selected embodiments, aspects or objects,disclosed herein or provided are novel or improved separators, batteryseparators, enhanced flooded battery separators, batteries, cells,and/or methods of manufacture and/or use of such separators, batteryseparators, enhanced flooded battery separators, cells, and/orbatteries. In accordance with at least certain embodiments, the presentdisclosure or invention is directed to novel or improved batteryseparators for enhanced flooded batteries. In addition, disclosed hereinare methods, systems and battery separators for enhancing battery life,reducing internal electrical resistance, increasing cold cranking amps,and/or improving uniformity in at least enhanced flooded batteries. Inaccordance with at least particular embodiments, the present disclosureor invention is directed to an improved separator for enhanced floodedbatteries wherein the separator has performance enhancing additives orcoatings, improved fillers, decreased tortuosity, increased wettability,reduced oil content, reduced thickness, decreased electrical resistance,and/or increased porosity, and where the use of such a separator in abattery reduces the water loss of the battery, lowers acidstratification of the battery, lowers the voltage drop of the battery,and/or increases the CCA of the battery. In accordance with at leastcertain embodiments, separators are provided that include or exhibitperformance enhancing additives or coatings, increased porosity,increased void volume, amorphous silica, higher oil absorption silica,fillers or silica with increased friability, increased ionic diffusion,higher silanol group silica, silica with an OH to Si ratio of 21:100 to35:100, silica with an OH to Si ratio of at least 27:100, reducedelectrical resistance, a shish-kebab structure or morphology, apolyolefin microporous membrane containing particle-like filler in anamount of 40% or more by weight of the membrane and ultrahigh molecularweight polyethylene having shish-kebab formations with extended chaincrystal (shish formation) and folded chain crystal (kebab formation) andthe average repetition periodicity of the kebab formation from 1 nm to150 nm, an average repetition periodicity of the kebab formation of 150nm or less, an average repetition periodicity of the kebab formation of120 nm or less, an average repetition periodicity of the kebab formationof 100 nm or less, having shish-kebab formations with extended chaincrystal (shish formation) and folded chain crystal (kebab formation) onat least the ribbed side and an average repetition periodicity of thekebab formation from 1 nm to 150 nm, decreased sheet thickness,decreased tortuosity, and/or the like, separators especially well-suitedfor enhanced flooded batteries, and/or the like.

In an exemplary embodiment of the present invention, a separator for alead acid battery is provided with a microporous membrane having apolyolefin polymer, a particle-like filler, and a processingplasticizer; wherein the particle-like filler is present in an amount of40% or more by weight; and wherein the polyethylene comprises polymer ina shish-kebab formation having a plurality of extended chain crystals(the shish formations) and a plurality of folded chain crystals (thekebab formations) and wherein the average repetition or periodicity ofthe kebab formations is from 1 nm to 150 nm, preferably less than 120nm. Further, the separator has a shelf life estimated static conductanceloss as compared to an initial value of less than approximately 9%, lessthan approximately 8%, less than approximately 7%, less thanapproximately 6%, and less than approximately 5%. One aspect of thepresent invention provides that the shelf life estimated staticconductance is measured at greater than 30 days of resting at standardconditions.

In certain embodiments, the average repetition or periodicity of thekebab formations is defined by: taking an image of the surface of thepolyolefin microporous membrane with a SEM, indicating at least threerectangular regions where the shish-kebab formation is continuouslyextended in the length of at least 0.5 μm or longer in the same SEMimage, and specifying the repetition or periodicity by Fourier Transformof contrast profile projected in the vertical direction to the lengthdirection of the each indicated rectangular region to calculate theaverage of the repetition periods.

In select embodiments, the filler is selected from the group consistingof silica, precipitated silica, fumed silica, and precipitated amorphoussilica; and wherein the molecular ratio of OH to Si groups within thefiller, measured by ²⁹Si-NMR, is within a range of from 21:100 to35:100, preferably 27:100 or more. In certain aspects of the presentinvention, silica is present at the kebab formations of polymer.

In certain selected aspects of the present invention, the microporousmembrane may be characterized by one of the following: a) an averagepore size of no greater than 1 μm; b) an electrical resistance less than75 mΩ·cm², or less than 70 mΩ·cm², or less than 65 mΩ·cm², or less than60 mΩ·cm², or less than 55 mΩ·cm², or less than 50 mΩ·cm², or less than45 mΩ·cm², or less than 40 mΩ·cm², or less than 35 mΩ·cm², or even less;c)an electrical resistance more than 20% less than an electricalresistance of a known separator for a flooded lead acid battery; d) aporosity greater than 50%; e) a final oil content of between about10-20% by weight, in some embodiments, about 14-20% by weight; and f)ribbing, serrated ribbing, embossed ribbing, and/or negative cross ribs;and combinations thereof.

In other aspects of the present invention, the microporous membrane maybe provided with a filler having high structural morphology. The fillermay be characterized by a) an average particle size of 5 μm or less; b)a surface area of at least 100 m²/g; c) an oil absorption rate of atleast 150 ml/100 mg, or combinations thereof.

The polyolefin polymer microporous membrane may be a polyolefin,polyethylene (such as, for example, ultra-high molecular weightpolyethylene), polypropylene, rubber, polyvinyl chloride, phenolicresins, cellulosic, synthetic wood pulp, glass fibers, synthetic fibers,natural rubbers, synthetic rubbers, latex, bisphenol formaldehyde, andcombinations thereof.

The microporous membrane may be provided with a filler to polymer weightratio of 1.5:1 to 6:1. The filler may be precipitated silica.Furthermore, the particle-like silica may be friable to such a degreethat after 30 seconds of ultra-sonication, the median silica particlesize is approximately 5.2 μm or less. In addition, the particle-likefiller may be friable to such a degree that after 60 seconds ofultra-sonication, the median silica particle size is approximately 0.5μm or less.

In some exemplary embodiments, exemplary embodiments of separators ofthe present invention may have one or more of the following: a mean poresize of at least approximately 120 nm; a diffusion coefficient of atleast approximately 1.6·10-10 at −5° C. and an electrical resistance ofapproximately 40 mΩ·cm² or lower; a diffusion coefficient of at leastapproximately 8.8·10-10 at 30° C., and an electrical resistance ofapproximately 40 mΩ·cm² or lower.

In certain embodiments of the present invention, a separator may beprovided with one or more of the following: a polyolefin microporousmembrane, wherein the polyolefin microporous membrane comprisespolyethylene, a particle-like filler, and a processing plasticizer,wherein the particle-like filler is friable to such a degree that after30 seconds of ultra-sonication, the median silica particle size isapproximately 5.2 μm or less; a polyolefin microporous membrane, whereinthe polyolefin microporous membrane comprises polyethylene, aparticle-like filler, and a processing plasticizer, wherein theparticle-like filler is friable to such a degree that after 60 secondsof ultra-sonication, the median silica particle size is approximately0.5 μm or less; a polyolefin microporous membrane, wherein thepolyolefin microporous membrane comprises polyethylene, a particle-likefiller, and a processing plasticizer, a diffusion coefficient of atleast approximately 1.6·10⁻¹⁰ at −5° C., and an electrical resistance ofapproximately 40 mΩ·cm² or lower; a polyolefin microporous membrane,wherein the polyolefin microporous membrane comprises polyethylene, aparticle-like filler, and a processing plasticizer, a diffusioncoefficient of at least approximately 8.8·10⁻¹⁰ at 30° C., and anelectrical resistance of approximately 40 mΩ·cm² or lower; a polyolefinmicroporous membrane, wherein the polyolefin microporous membranecomprises polyethylene, a particle-like filler, and a processingplasticizer, a diffusion coefficient of at least approximately 1.6·10⁻¹⁰at −5° C., and the particle-like filler is friable to such a degree thatafter 30 seconds of ultra-sonication, the median silica particle size isapproximately 5 μm or less; a polyolefin microporous membrane, whereinthe polyolefin microporous membrane comprises polyethylene, aparticle-like filler, and a processing plasticizer, a diffusioncoefficient of at least approximately 8.8·10⁻¹⁰ at 30° C., and theparticle-like filler is friable to such a degree that after 60 secondsof ultra-sonication, the median silica particle size is approximately0.5 μm or less; a polyolefin microporous membrane, wherein thepolyolefin microporous membrane comprises polyethylene, a particle-likefiller, and a processing plasticizer, a diffusion coefficient of atleast approximately 1.6·10⁻¹⁰ at −5° C., and a mean pore size of atleast approximately 120 nm; and a comprises polyethylene, aparticle-like filler, and a processing plasticizer, a diffusioncoefficient of at least approximately 8.8·10⁻¹⁰ at 30° C., a mean poresize of at least approximately 120 nm; and combinations thereof.

The separator above wherein the separator comprises at least one of:

-   -   one or more of a surfactant, coating, wetting agent, colorant,        antistatic additive, antioxidant, agent for reducing oxidation,        and combinations thereof; and at least one surfactant, wherein        such surfactant is a non-ionic surfactant, an anionic        surfactant, or a combination thereof.

In accordance with at least certain aspects of the present invention,lead acid batteries may be provided utilizing separators as generallydescribed herein.

In particular embodiments disclosed herein, a lead acid battery may beprovided with a polyolefin microporous membrane having polyethylene,preferably, ultrahigh molecular weight polyethylene, a particle-likefiller, and a processing plasticizer; wherein the particle-like filleris present in an amount of 40% or more by weight; and wherein thepolyethylene comprises polymer in a shish-kebab formation having aplurality of extended chain crystals (the shish formations) and aplurality of folded chain crystals (the kebab formations) and whereinthe average repetition or periodicity of the kebab formations is from 1nm to 150 nm, preferably less than 120 nm. The battery may further beprovided with a shelf life estimated cold cranking amps loss as comparedto an initial value of less than approximately 9%, less thanapproximately 8%, less than approximately 7%, less than approximately6%, and less than approximately 5%. One aspect of the present inventionprovides that the shelf life estimated static cold cranking amps ismeasured at greater than approximately 30 days of resting at standardconditions.

In select embodiments of the present invention, the lead acid batterymay be any one of the following: a flat-plate battery, a flooded leadacid battery, an enhanced flooded lead acid battery, a deep-cyclebattery, an absorptive glass mat battery, a tubular battery, an inverterbattery, a vehicle battery, a SLI battery, an ISS battery, an automobilebattery, a truck battery, a motorcycle battery, an all-terrain vehiclebattery, a forklift battery, a golf cart battery, a hybrid-electricvehicle battery, an electric vehicle battery, an e-rickshaw battery, ane-trike battery, and an e-bike battery.

In accordance with at least certain aspects of the present invention,vehicles may be provided utilizing batteries and separators as generallydescribed herein.

In particular embodiments disclosed herein, a vehicle may be providedwith a lead acid battery having a polyolefin microporous membrane havingpolyethylene, preferably, ultrahigh molecular weight polyethylene, aparticle-like filler, and a processing plasticizer; wherein theparticle-like filler is present in an amount of 40% or more by weight;and wherein the polyethylene comprises polymer in a shish-kebabformation having a plurality of extended chain crystals (the shishformations) and a plurality of folded chain crystals (the kebabformations) and wherein the average repetition or periodicity of thekebab formations is from 1 nm to 150 nm, preferably less than 120 nm.The battery may further be provided with a shelf life estimated coldcranking amps loss as compared to an initial value of less thanapproximately 9%, less than approximately 8%, less than approximately7%, less than approximately 6%, and less than approximately 5%. Oneaspect of the present invention provides that the shelf life estimatedstatic cold cranking amps is measured at greater than approximately 30days of resting at standard conditions.

In select embodiments of the present invention, the vehicle may be oneof the following: an automobile, a truck, a motorcycle, an all-terrainvehicle, a forklift, a golf cart, a hybrid-electric vehicle, an electricvehicle, an e-rickshaw, an e-trike, and an e-bike.

In accordance with at least certain aspects of the present invention, asystem may be provided utilizing batteries, separators, and batteryanalyzers as generally described herein.

In particular embodiments disclosed herein, a system may be providedwith a lead acid battery having a polyolefin microporous membrane havingpolyethylene, preferably, ultrahigh molecular weight polyethylene, aparticle-like filler, and a processing plasticizer; wherein theparticle-like filler is present in an amount of 40% or more by weight;and wherein the polyethylene comprises polymer in a shish-kebabformation having a plurality of extended chain crystals (the shishformations) and a plurality of folded chain crystals (the kebabformations) and wherein the average repetition or periodicity of thekebab formations is from 1 nm to 150 nm, preferably less than 120 nm.The system may further be provided with a battery analyzer capable ofmeasuring battery conductance. The battery may further be provided witha shelf life estimated cold cranking amps loss as measured by saidbattery analyzer, and as compared to an initial value, of less thanapproximately 9%, less than approximately 8%, less than approximately7%, less than approximately 6%, and less than approximately 5%. Oneaspect of the present invention provides that the shelf life estimatedstatic cold cranking amps is measured at greater than approximately 30days of resting at standard conditions.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide improved batteryseparators, high conductance separators, improved lead-acid batteries,such as flooded lead-acid batteries, high conductance batteries, and/or,improved vehicles including such batteries, and/or methods ofmanufacture or use of such separators or batteries, and/or combinationsthereof; improved lead acid batteries incorporating the improvedseparators and which exhibit increased conductance; lead acid batteryseparators having structure or features, or topological featuresdesigned to provide membranes with improved conductance, low ER, lowwater loss, and/or the like, and/or particular, non-limiting examplesmay include lead acid battery separators having structure or featuresdesigned to improve battery conductance, lower ER, lower water loss,and/or the like.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide an improved conductancebattery separator comprising a microporous polymeric membrane providinghigh conductance, wherein the membrane comprises one selected from thegroup consisting of: Low ER, Low Water Loss, a profile providing limitedcontact with or obstruction of the positive plate or PAM, a profileproviding a large acid volume adjacent the positive plate or PAM, andcombinations thereof.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide an improved separator,improving the membrane-electrode contact and continuity, improving themembrane-electrode interfacial resistance, improving conductivity,providing lead acid batteries that exhibit reduced conductivity lossover time, providing improved battery components, and combinationsthereof.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide an improved highconductance battery.

In accordance with at least selected embodiments, aspects, or objects,the present disclosure or invention may provide improved batteryseparators, high conductance separators, improved lead-acid batteries,such as flooded lead-acid batteries, high conductance batteries,improved vehicles including such batteries, methods of manufacture oruse of such separators or batteries, improved lead acid batteriesincorporating the improved separators and which exhibit increasedeffective static conductance, and combinations thereof as shown ordescribed herein.

In accordance with at least selected embodiments, the present disclosureor invention is directed to improved battery separators, highconductance separators, improved lead-acid batteries, such as floodedlead-acid batteries, high conductance batteries, and/or, improvedvehicles including such batteries, and/or methods of manufacture or useof such separators or batteries, and/or combinations thereof. Inaccordance with at least certain embodiments, the present disclosure orinvention is directed to improved lead acid batteries incorporating theimproved separators and which exhibit increased conductance. Particular,non-limiting examples may include lead acid battery separators havingstructure, features, or topological features designed to improveconductance, low ER membranes, low water loss membranes, and the like.In accordance with at least selected embodiments, the present disclosureor invention is directed to improved lead acid batteries that do notsuffer substantial conductivity loss over time, improved batterycomponents, including separators that provide lead-acid batteries thatdo not exhibit conductivity loss or exhibit a reduced conductivity lossover time, improved systems or cells, and/or the like.

The present invention may be embodied in other forms without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the invention.

The foregoing written description of structures and methods has beenpresented for purposes of illustration only. Examples are used todisclose exemplary embodiments, including the best mode, and also toenable any person skilled in the art to practice the invention,including making and using any devices or systems and performing anyincorporated methods. These examples are not intended to be exhaustiveor to limit the invention to the precise steps and/or forms disclosed,and many modifications and variations are possible in light of the aboveteaching. Features described herein may be combined in any combination.Steps of a method described herein may be performed in any sequence thatis physically possible. The patentable scope of the invention is definedby the appended claims, and may include other examples that occur tothose skilled in the art. Such other examples are intended to be withinthe scope of the claims if they have structural elements that do notdiffer from the literal language of the claims, or if they includeequivalent structural elements with insubstantial differences from theliteral language of the claims.

-   -   001 The compositions and methods of the appended claims are not        limited in scope by the specific compositions and methods        described herein, which are intended as illustrations of a few        aspects of the claims. Any compositions and methods that are        functionally equivalent are intended to fall within the scope of        the claims. Various modifications of the compositions and        methods in addition to those shown and described herein are        intended to fall within the scope of the appended claims.        Further, while only certain representative compositions and        method steps disclosed herein are specifically described, other        combinations of the compositions and method steps also are        intended to fall within the scope of the appended claims, even        if not specifically recited. Thus, a combination of steps,        elements, components, or constituents may be explicitly        mentioned herein or less, however, other combinations of steps,        elements, components, and constituents are included, even though        not explicitly stated.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. Ranges may be expressed herein as from “about” or“approximately” one particular value, and/or to “about” or“approximately” another particular value. When such a range isexpressed, another embodiment includes from the one particular valueand/or to the other particular value. Similarly, when values areexpressed as approximations, by use of the antecedent “about,” it willbe understood that the particular value forms another embodiment. Itwill be further understood that the endpoints of each of the ranges aresignificant both in relation to the other endpoint, and independently ofthe other endpoint. “Optional” or “optionally” means that thesubsequently described event or circumstance may or may not occur, andthat the description includes instances where said event or circumstanceoccurs and instances where it does not.

Throughout the description and claims of this specification, the word“comprise” and variations of the word, such as “comprising” and“comprises,” means “including but not limited to,” and is not intendedto exclude, for example, other additives, components, integers, orsteps. The terms “consisting essentially of” and “consisting of” can beused in place of “comprising” and “including” to provide for morespecific embodiments of the invention and are also disclosed.“Exemplary” means “an example of” and is not intended to convey anindication of a preferred or ideal embodiment. Similarly, “such as” isnot used in a restrictive sense, but for explanatory or exemplarypurposes.

Other than where noted, all numbers expressing geometries, dimensions,and so forth used in the specification and claims are to be understoodat the very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, to be construed inlight of the number of significant digits and ordinary roundingapproaches.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meanings as commonly understood by one of skill in the artto which the disclosed invention belongs. Publications cited herein andthe materials for which they are cited are specifically incorporated byreference.

Additionally, the invention illustratively disclosed herein suitably maybe practiced in the absence of any element which is not specificallydisclosed herein.

1-45. (canceled)
 46. A lead acid battery comprising: polyolefinmicroporous membrane comprising polyethylene; a particle-like filler; aprocessing plasticizer; wherein the particle-like filler to polyethyleneweight ratio is present in an amount from 1.5:1 to 6:1; an optimizedprofile with a rib surface area, compared with a rib surface area of aconventional rib profile such as a solid vertical rib profile, that is10-90% of said conventional rib surface area, preferably 30-70% of saidconventional rib surface area, and more preferably, in some instances,40-60% of said conventional rib surface area; said microporous membranehaving a shelf life estimated cold cranking amps loss as compared to aninitial value of less than approximately 9%; and-optionally, wherein themicroporous membrane is characterized by one or more the following: amean pore size of at least approximately 120 nm; a diffusion coefficientof at least approximately 1.6·10-10 at −5° C., and an electricalresistance of approximately 40 mΩ·cm2 or lower; a diffusion coefficientof at least approximately 8.8·10-10 at 30° C., and an electricalresistance of approximately 40 mΩ·cm2 or lower;
 47. The lead acidbattery according to claim 46, wherein said shelf life estimated coldcranking amps loss as compared to an initial value of less thanapproximately 8%.
 48. The lead acid battery according to claim 46,wherein said shelf life estimated cold cranking amps loss as compared toan initial value of less than approximately 7%.
 49. The lead acidbattery according to claim 46, wherein said filler is selected from thegroup consisting of silica, precipitated silica, fumed silica, andprecipitated amorphous silica.
 50. The lead acid battery according toclaim 46, wherein said optimized profile is characterized by one fromthe group consisting of: ribbing, serrated ribbing, embossed ribbingand/or negative cross ribs and combinations thereof.
 51. The lead acidbattery according to claim 46, wherein said shelf life estimated coldcranking amps is measured at greater than approximately 30 days ofresting at standard conditions.
 52. The lead acid battery according toclaim 46, wherein said battery is selected from the group consisting of:a flat-plate battery, a flooded lead acid battery, an enhanced floodedlead acid battery, a deep-cycle battery, an absorptive glass matbattery, a tubular battery, an inverter battery, a vehicle battery, aSLI battery, an ISS battery, an automobile battery, a truck battery, amotorcycle battery, an all-terrain vehicle battery, a forklift battery,a golf cart battery, a hybrid-electric vehicle battery, an electricvehicle battery, an e-rickshaw battery, an e-trike battery, and ane-bike battery.
 53. A vehicle comprising a lead acid battery accordingto claim 52, wherein said vehicle comprises one from the groupconsisting of: an automobile, a truck, a motorcycle, an all-terrainvehicle, a forklift, a golf cart, a hybrid-electric vehicle, an electricvehicle, an e-rickshaw, an e-trike, and an e-bike.